ORGANIC CHEMISTRY

COURSE OUTLINE:
➢ Definition of organic Chemistry
➢ Properties of organic compounds
➢ Functional groups of organic compounds
➢ Molecular empirical structural formulae
➢ Homologous series (Groups of organic compounds)
➢ Alkanes
➢ Alkener Hydro carbons
➢ Alkynes
➢ Alkyl halides (Halogeno alkanes)
➢ Alcohols
➢ Ethers
➢ Phenols
➢ Benzene
✓ Methy/Benzene
✓ Nitrobenzene Aromatics
✓ Chlorobenzene
➢ Carbons/compounds
✓ Aldehydes (Alkanals)
✓ Ketones (Alkanones)
➢ Carboxylic acids
✓ Acidic halides (Alkanoy chlorides)
✓ Amides
➢ Esters
➢ Amines
➢ Diazonium salts
➢ Applied organic chemistry
➢ Practical organic chemistry

Reference books:
Principles of Organic Chemistry
A’ level Chemistry – Ramsden.

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INTRODUCTION:
Definition of Organic Chemistry:
Organic Chemistry is the Chemistry of Carbon and related elements. It does not
involve inorganic compounds of carbon like CO2, 𝐶𝑂32− 𝑠, 𝐻𝐶𝑂3− s.

Organic Chemistry started when the first organic compounds were largely
obtained from living things. This therefore makes carbon as the most abundant
element in living organisms.

PROPERTIES OF ORGANIC COMPOUNDS:

Organic compounds are characterized by the following properties:
• They are made up of carbon and other elements like H2, O2, N2, S, P and Cl2.
• They are complex in structure e.g. some are made up of long chains of
carbon, highly branched chain, rings of carbon.
• They exhibit isomerism a condition in which several structures can be
written from one molecular formula.
• All organic compounds are bonded by covalent bonding.
• Most organic compounds undergo slower reactions.
• From the above properties, organic chemistry places a lot of interest in the
behaviour of carbon.

Carbon as an element in organic chemistry:

C(6) = 2:4 1S22S22P2
Electronic configuration

From the above configuration, carbon has got two principle equation numbers, a
total of 6 electrons.

2 electrons in the S-orbital (inner energy level).

4 electrons in the 2nd principle quantum number distributed as 2 in the S-orbital
and 2 in P-orbital.

When carbon undergoes a chemical reaction, it uses all the four electrons in the
P-quantum number which gives it a tetravalent.

Since bonding in organic compounds occurs in covalent bond (sharing electrons),

it means each carbon atom should contribute four (2 pairs of electrons). Carbon
then forms 4 covalent bonds by molecular mixing of orbitals a process known as
Hybridization.

2
HYBRIDIZATION OF ORBITALS IN CARBON
S S P
C (ground state-uncreative)

When carbon atom is excited, one electron from the 2S – orbital is sent to the 2P
giving in total four unpaired electrons which now become the tetravalent of
carbon.

Bonding in carbon thereof involves the mixing of the S – and the P-orbitals.

(i) Formation of alkanes (Example methane).

Bonding in alkanes involves 2SP3 hybridization.
H
|
H C H C 1S 2S 2P
|
H

H H H H

(ii) Bonding in alkenes

In alkenes, bonding involves 2Ps hybridization.

Ethene:
H H
| |
C = C
| |
H H H H

H H

3
(iii) Bonding in alkynes
2SP hybridization e.g. ethyne
i.e. 1 electron in 2S of each carbon atom combines to form a normal sigma
bond while each hydrogen combines with each of the 2SP electron leaving
2 unpaired electrons in the 2P which will overlap to form 2𝜋 bonds.

H C C H

H C≡C H

UNIQUE PROPERTIES OF CARBON

Carbon is generally a unique element and it displays the following properties:
(i) If forms multiple bonds with other elements or itself. E.g.
– double bond C = C (alkene); C = O (carbons)
- triple bond C≡C (alkynes); C≡N (Nitriles)

Carbon forms up to 4 covalent bonds and this is always exhibited in all its
compounds.

-C- -C = C - -C ≡ C – - C ≡ N.

Carbon forms long chain compounds a process known as catenation, e.g.

- C – C – C – C -.

Carbon rings and branded compounds.

C
C C -C-
-C–C–C
C C
C

4
 FUNCTIONAL GROUP:
Is an atom or groups of atoms in an organic compound that determines the
chemical properties of that compound.

Most of the chemical reactions of organic compounds are determined by their

functional group.

Families of organic compounds known as homologous series are also determined

by functional group.
No. Homologous series Functional group Examples
(class)
1. Alkanes 𝐶𝑛 𝐻2𝑛+2 - C – C – (Carbon single 𝐶𝐻4 (Methane)
(R – H) bond)
2. Alkenes (𝐶𝑛 𝐻2𝑛 ) - C = C – (Carbon double 𝐶2 𝐻4 (Ethene)
bond)
3. Alkynes (𝐶𝑛 𝐻2𝑛+2 ) - C ≡ C – (Carbon triple 𝐶2 𝐻2 (Ethyne)
bond)
Alkyl halides/halogenal
alkaner (R–x)
4. 𝐶𝑛 𝐻2𝑛+1 X Halogen(X) 𝐶2 𝐻5 𝐶𝑙(Chloro ethane)
Where X is a halogen e.g.
Cl2, Br.
5. Alkanals (alcohols) Hydroxyl group 𝐶3 𝐻7 𝑂𝐻(Propanol)
(𝐶𝑛 𝐻2𝑛+1 𝑂𝐻)(𝑅 − 𝑂𝐻 (-OH)
6. Ethers (R-OR) - O – (Oxygen) 𝐶2 𝐻6 𝑂 H H
H–C–O–C–H
H H

7. Carbons/Compounds O 𝐶2 𝐻4 H O
(i) Alkanals (aldehydes) - C – H (Carbony/Carbon H–C–C–H
& H2) H
(Ethanal)
(ii) Alkanones (Ketone) O 𝐶3 𝐻6 𝑂 (Propanone)
O - C – (Carbony/Carbon) H H
R–C–R H–C–C–C–H
H O H

5
8. Carboxylic acid O 𝐶2 𝐻4 𝑂2 (𝐸𝑡ℎ𝑎𝑛𝑜𝑖𝑐 𝑎𝑐𝑖𝑑)
R – COOH -C–O–H H O
Carboxylic acid group H–C–C–O–H
H
9. Esters (ROOR) O 𝐶3 𝐻6 𝑂2 (𝑀𝑒𝑡ℎ𝑦𝑙 𝑒𝑡ℎ𝑎𝑛𝑜𝑎𝑡𝑒)
-C–O– H O H
H–C–C-O–C–H
H H H
10. Nitro compound −𝑁𝑂2 (𝑁𝑖𝑡𝑟𝑜 𝑔𝑟𝑜𝑢𝑝) 𝐶2 𝐻4 𝑁𝑂2 (𝑁𝑖𝑡𝑟𝑜 𝑒𝑡ℎ𝑎𝑛𝑒)
R - 𝑁𝑂2 H H
H – C – C - 𝑁𝑂2
H H
11. Nitriles (Cyanohydrins) −𝐶 ≡ 𝑁(𝑁𝑖𝑡𝑟𝑖𝑙𝑒 𝑔𝑟𝑜𝑢𝑝) Ethanitrile 𝐶2 𝐻3 𝑁
R - C≡N H
H–C–C≡𝑁
H
12. (Acid halides) O 𝐶2 𝐻3 𝑂4 𝐶𝑙
O C–X H O
R – CO – X H–C–C–X
H
(Ethanoyl)
13. Amides O 𝐶2 𝐻5 − 𝑂𝑁
O - C - 𝑁𝐻2 H O
R – C - 𝑁𝐻2 (Amide group) H – C – C 𝑁𝐻2
H
(Ethanimide)
14. Amines −𝑁𝐻2 (𝐴𝑚𝑖𝑛𝑜 𝑔𝑟𝑜𝑢𝑝) H
(𝑅 − 𝑁𝐻2 ) H – C - 𝑁𝐻2
H
𝐶𝐻5 𝑁 (𝑀𝑒𝑡ℎ𝑦𝑙 𝑎𝑚𝑖𝑛𝑒)

6
 EMPIRICAL MOLECULAR AND STRUCTURAL FORMULAE

Empirical formula is the simplest formula which expresses the ratio of the
number of atoms present in a molecular or compound. E.g.
A certain organic compound has 39.13% by mass Carbon 52.23%, Oxygen and
the rest hydrogen, determine its empirical formula.
39.13 + 52.23
100 – 91. 36 = 8.64

Element C H O
Percentage composition 39.13 8.64 52.23
Composition 39.13 8.64 52.23
Rfm 12 1 16

Number of moles 3.2608 8.64 3.2644

Divide by smallest 3.2608 8.64 3.2644
3.2608 3.2608 3.2608

Mole ratio 1x2 2.6 x 2 1x2 1 x 3 2. 6 x 3 1x3

1 5.3 1 𝐶3 𝐻8 𝑂3

∴ Empirical formula = 𝐶2 𝐻5 𝑂2.

Molecular formula expresses the true or actual number of each atom present in
1mole of a compound. It is also a multiple of an empirical formular.

𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑚𝑎𝑠𝑠

= 𝑛 , 𝑛 = simple whole number.
𝐸𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎𝑟 𝑚𝑎𝑠𝑠

Molecular formula = [Empirical formula].

MOLECULAR FORMULA MASSES:

They can be determined from;
(i) Vapour density:
When a compound is vapourized and weighed, its mass is twice the
molecular formula mass.
2 x V.P = MFM.

7
(ii) Rates of diffusion (Graham’s law)
𝑅
𝑀𝐹𝑀𝐴 = 𝐴 2 x 𝑀𝐹𝑀𝐵
𝑅𝐵

(iii) Ideal gas equation

𝑚𝑅𝑇
PV = nRT; PV =
𝑚𝑅
𝑚𝑅𝑇
Mr =
𝑃𝑉

GASEOUS HYDROCARBONS (EUDIOMETRY)

Eudiometry is a technique used to determine molecular formula of gaseous
hydrocarbons.

When a gaseous hydrocarbon is exploded with excess oxygen, it readily burns

forming 𝐶𝑂2 𝑎𝑛𝑑 𝐻2 𝑂 as the only product.

If the gases are passed over an alkali e.g. (KOH or NaOH), all the CO2 formed is
absorbed and the diminution (reduction) in the volume of the gases is due to
CO2.

The residual gas at that point will now be excess O2.

The volume of H2O formed is regarded as negligible.

𝑥+𝑦 𝑥
CxHy (g) + 𝑂2 (g) X𝐶𝑂2 (𝑔) + 𝐻2 𝑂(𝑙)
4 2

From the above equation, everyone mole of a hydrocarbon is equivalent to X

moles of 𝐶𝑂2 produced.

Similar when the volumes are related, the volume at CO2 is equivalent to (X) x
volume of CO2 produced.

X (Volume of H.C) = Volume of CO2 produced.

Then the volume of O2 used can also be related to the volume of the hydrocarbon
by volume of;
𝑥+𝑦
Oxygen used = ( ) (Volume of hydrocarbon).
4

8
Example:
15𝑐𝑚3 of a gaseous hydrocarbon were exploded with 105𝑐𝑚3 of oxygen in a
sealed vessel after cooling, the residual volume occupies 75𝑐𝑚3 . On addition of
caustic potash, there was a final diminution/decrease of volume to 30𝑐𝑚3 .
Determine the molecular mass of a hydrocarbon.

Let the hydrocarbon be 𝐶𝑥 𝐻𝑦 .

𝑥+𝑦 𝑦
𝐶𝑥 𝐻𝑦(𝑔) + ( ) 𝑂2(𝑔) 𝑋𝐶𝑂2(𝑔) + 𝐻2 𝑂(𝑙)
4 2

Volume of 𝑂2 used = 105 – 30 = 75𝑐𝑚3

Volume of 𝐶𝑂2 produced = 75 – 30 = 45𝑐𝑚3
𝐶𝑥 𝐻𝑦 = volume of 𝐶𝑂2 produced.
= 45.
45
= 3.
15

(𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐻𝐶 ) x + y = Volume of 𝑂2 used.

4
15 3 + y = 75 3+y =5
4 4
y
3 + y = 75 4 =2
4 15 y = 8.
Molecular formula is 𝐶3 𝐻8
12 x 3 + 8 x 1 = 449.

9
DETERMINATION OF MOLECULAR FORMULA OF ORGANIC
COMPOUND USING MASS OF 𝑪𝑶𝟐 𝒂𝒏𝒅 𝑯𝟐 𝑶.

When an organic compound is burnt, the masses of the products, carbon dioxide
and H2O together with the initial mass of the organic compound can be used to
determine the molecular formula.

Example:
0.464g of an organic compound Q when burnt gave 1.32g of CO2, 0.315g of H2O.
When 0.2325g of Q were separately burnt, 7.08 cm3 of N2 gas at s.t.p was
produced. Determine the molecular formula of Q and draw its structure. Vapour
density = 46.5.

Organic cpd + O2 CO2 + H2O

12g of C 44g of CO2
2g of H 18g of H2O.

12g of carbon produces 44g of CO2.

Xg of carbon produce 1.32g of CO2.

12
( 𝑥 1.32) 𝑔 of carbon inorganic compound.
44
= 0.36g.
0.36
Percentage of carbon = 𝑥 100
0.464

= 77.6%

2g of H2 in Q produces 18g of H2O.

y of H2 in Q produces 0.315g of H2O.
2
y = ( 𝑥 0.315) 𝑔 of 𝐻2
18
= 0.035g.

0.035
Percentage of H in Q = 𝑥 100
0.464

= 7.5%

Mass of Nitrogen = 0.36 + 0.035 = 0.395

0.464 – 0.395
= 0.069g of N2.

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Percentage of N2 = 77.6 + 7.5 = 85.1g
(100 – 85.1)
= 14.9%

1moleof a gas contains 22400cm3 at s.t.p.

Moles of N2 contains 7.08cm3.
7.08
22400 = 3.16 x 10-4moles.

0.2325g of Q produces 3.16 x 10-4 moles of N2.

Xg of Q produced by 1mole of N2.

Elements C H N
Percentage composition 776. 7.5 14.9
77.6 7.5 14.9
Relative atoms
12 1 14

Moles 6.47 7.5 1.06

6.47 7.5 1.06
Simple ratio
1.06 1.06 1.06

Simple ratio 6 7 1
Empirical formula 𝐶6 𝐻7 𝑁
(𝐶6 𝐻7 𝑁)𝑛 = 46.5 𝑥 2
n(12 x 6) + 7 x 1 + 14 = 93
93n = 93
n = 1. Molecular formula = 𝐶6 𝐻7 𝑁

11
 H–N–H
C
H H
C C
Phenyl-amine.
C C
H H
C
H

STRUCTURAL FORMULA
It shows the different atoms and how they are connected in one molecule of a
compound e.g.
1. Ethane structure.
H H
H – C – C – H or H3C.CH3
H H

2. Nitrobenzene (C6H5NO2).
H
C
H–C C–N–O

C C O
H H
C
H

3. Propane (C3H8)
H H H
H – C – C – C - or H3C – C H2 CH3
H H H

12
4. But-2-ene (C4H8)
H H H H
H–C–C=C–C–H or H3C CH = CH CH3
H H

5. Buta-1,3-diene
H H H
H–C=C–C=C–H or H2C = CH CH = CH2
H

ORGANIC COMPOUNDS
Organic compounds are generally classified according to the functional groups
they do have and its very important that all the organic compounds are given
names.

NOMENCLATURE OF ORGANIC COMPOUNDS

Naming of organic compounds follows a strict system of nomenclature where
names are assigned.

NAMING OF HYDRO CARBONS

They are named using “stem” names that indicate the alkyl groups. E.g.

Alkyl group: Name:

+𝐶𝐻3 1 Methyl
+𝐶𝐻2𝐶𝐻3 2 Ethyl
+𝐶𝐻2𝐶𝐻2𝐶𝐻3 3 Propyl
+𝐶𝐻2𝐶𝐻2𝐶𝐻2𝐶𝐻3 4 Butyl
−𝐶6 𝐻5 or 6 Phenyl

13
RULES GOVERNING NOMENCLATURE (Guidelines)
(i) Hydrocarbons are named as derivatives of alkanes. Where the suffix-ane-
is added to the stem name.

(ii) Always identify the longest continuous chain in the compound and this
gives the parent name. Other things attached to that chain are regarded as
branches. E.g.
H3C CH.CH2CH3 but-4carbon atoms.
CH3 Branch

(iii) Number – the carbon parent chain from one end to the other end giving
the position of the branch the lowest number. E.g.

H3C CH CH2 CH3

CH3

(iv) If there are more than one substituent branch, the numbering has to
consider the lowest sum of the positions. E.g.
CH3
H3C CH CH CH CH CH3
CH3

R – L – sum of branches = 4 + 5 = 9.
L – R, sum of branches = 2 + 3 selected.
=5
The sum of the locants moving from left to right is the lowest and therefore
it is preferred.

(v) All the positions of the locants are identified and they are put as prefix
separated with a (-) in the branch. E.g.
2 – methyl
3 – methyl

(vi) When there is more than one substituent, the following is noted:

14
 (a) Similar substituents are given a prefix di – 2, tri – 3, tetra – 4 ---- and
their locants are also indicated before the prefix but the locant
separated by a comma (,). E.g. 2, 3-dimethyl.
The numerical order of the locants is followed.
CH2 CH3
H3C CH – CH CH2 CH2 CH3 hex – 6 carbon atoms.
CH3
3 – Ethyl
2 – Methyl

The alphabets in the beginning letter of the names of the substituent

has got to be followed.

(vii) The last name to be written is the parent name which indicates the number
of carbon atoms in the chain.
CH3 CH2 CH3
H3CCH2 C CH2 CH CH2 CH3
CH3
3, 3-dimethyl -5-ethyl heptane.

If a multiple bond (triple or double bond) is present, then the longest chain
identified must involve the (double or triple) bond.

The multiple bond must be given the lowest number within the stem
name.
H3C CH2 CH = C – CH2CH3
CH2
CH2
CH3
4-ethyl hept-3-ene.

(viii) When there are other functional groups, their positions, names are
indicated. E.g. Halogen (Cl, F, Br, I) = Choro, Fluoro, Bromo, Iodo.
OH = (alcohol) – Ol
C = C (double bond) – ene
C≡C (triple bond) – yne.

15
 O
C – H (aldehyde) – anal

O
C (Ketone) – one

−𝑁𝐻2 (amine) – amine.

(ix) VOWEL/CONSONANT RULE

When naming a compound where a locant is included within the stem
name, the two letters close to the locant must be a vowel and a consonant
and not all vowels or all consonants. E.g.
CH3CH CH3 Propan – 2 - Ol
OH Consonant Vowel

CH3 CH = CHCH = CH2 Penta – 1, 3-diene.

HOCH2CH2 OH Ethane-1, 2-diol.

HOOC.COOH Ethane-1, 2-dioc acid.

CH3COOH Ethanoic acid.

(x) When naming compounds with very many functional groups (poly
functional compounds), the functional groups are assigned an order
depending of the seniority order and this order is the carboxylic acid,
carbonyl, cyanide, ketone, alcohol, amines, double bond, triple bond, nitro
group and halogen.
O O
- COOH > C – H > C≡N > C > -OH > -NH2 > –C=C->
Katone Hydroxyl
C≡C > NO2 > X(halogen).
E.g. CH3CH CH2 COOH
Cl 3 – chloro butanoic acid.

NH2
CH3CH – CH CH = CH2
Cl 4-chloro-3-amino pentene.

16
H2C = CHCH2CH2C≡CH
Hexene-5-yne.

For the case of cyclic compounds (ringed compounds), the prefix “cyclo) is
added to the parent alkane name.
CH2
Cyclopropane Cyclobutane
H2C CH2

Cyclopentane Cyclohexene

Cyclohexa-1, 3, 5 – triene.
Or
Benzene (Phenyl group)

STRUCTURES OF ORGANIC COMPOUNDS FROM NAMES:

Structures can be written from the names.

Example:
Butane
H H H H
H–C–C–C–C–H Or H3C CH2 CH3 CH3
H H H H

2-Methyl propane.
H
H H- C - H CH3
H-C – C–C–H Or H3C CH CH3
H H H

5-methyl hept-3-ene.
H
H H H H–C–H H
H–C–C–C=C–C–C–C–H
H H H H H H
17
 CH3
H3C CH2 CH = CH CHCH2 CH3

3, 4-dimethyl pentanol.
H H
H H H–C–H H–C–H
OH – C - C- C - C- C-H

H H H H H

4, 5-dimethyl hex-2-yne.
H
H H–C–H H H
H–C –C ≡ C– C– C – C–H
H H H–C–H H
H

Ethane-1, 2 – diol
H H
OH – C – C – OH
H H

Phenyl methanol
CH2OH

2-phenyl ethanol

CH2CH2OH

2, 2 –dimethyl propane
CH3

18
 H3C.C.CH3
CH3
Propane- 1, 2, 3 – triol.
HO.CH2 CH CH2 Or: H2C(OH)CH(OH)CH2.OH
OH OH

Or: H H H
H–C–C– C–H
OH OH OH

International Union of Pure and Applied Chemistry.

N.B: Name organic compounds should always consider the IUPAC system.
Where names and systematically written and this is the most universally
known way of naming. However, trivial names may be found in a number
of books and these should not be used for exam purposes.

E.g. CH≡CH (Ethyne) = (Acetylene) trivial name.

CH3CH2CH2OH Propanol = (Propyl alcohol) trivial name.

ISOMERISM
This is the existence of compounds with the same molecular formula but
different structural formulae. These compounds are known as Isomers.

Types of isomerism
There are two types of isomerism with a number of subtypes.
1. Structural isomerism
The type of isomerism where compounds differ in the arrangement of
atoms within the molecule i.e. isomers under structural isomerism differ in
the carbon skeleton.

2. Stereo isomerism
Type of isomerism where compounds of the same molecular formula and
structural formula differ in the spatial arrangement of atoms.

STRUCTURAL ISOMERISM
Structural isomers can be further subdivided into:
(i) Chain structural isomerism

19
 This is where compounds differ in the arrangement of carbon atoms in a
molecule.
Note: The position of the functional group in the chain must remain the same.
E.g. (C4H10)
H3C CH2CH2 CH3 n-Butane

CH3
H3C CH CH3 2-methyl (propane).

C5H12

H3C CH2 CH2CH2 CH3 𝑛- pentane

H3C CH2 CH CH3 3-methyl (butane)

CH3

CH3
H3C – C – CH3
CH3

(ii) Functional isomerism

Type of isomerism where the isomers differ by the functional group. Such
isomers also differ in both physical and chemical properties. E.g. Alcohols.
- Ethers are isomeric.
C2H6O
H3C CH2 OH Ethanol.
H3COCH3 Dimethyl ether.

- Alkenes and cyclic alkanes

(C3H6)
H3C CH = CH2 Propane

CH2

H2C CH2 Cyclopropane.

20
 - Carboxylic acids and esters.
C4H8O2
H3C CH2 CH2 COOH Butanoic acid

O
H3C C – O CH2 CH3 Ethyl ethanoate (ester)

(iii) Positional isomerism

Type of isomerism where the compounds with the same molecular
formula differ in position of the functional group within the same carbon
skeleton.
- (C3H7OH)
H3C CH2 CH2OH Propan-1-Ol

H3C CH CH3 Propan-2-Ol

OH

- C 4H 8
H3C CH2 = CH2 CH3 But-2-ene
H2C = CH CH2 CH3 But-1-ene

- (C4H9Cl)
H3C CH CH CH – Cl Chloro butane
H3C CH(Cl) CH2 CH3 2-Chloro butane

Question:
Write all the isomers of the compounds with molecular formula C5H12O.
1. H3C CH2 CH2 CH2 CH2 OH 𝑛 – Pent-1-ol

2. CH3 CH2 CH2 CH CH3 Pentan-2-ol

OH

3. CH3 CH2 CH CH2 CH3 Pentan-3-ol

OH

4. CH3 CH CH2CH2 OH 3-methyl butanol

21
5. CH3
CH3 C.CH2 OH 2, 2-dimethyl propanol
CH3

6. CH3 CH2 CH CH2 OH 2-methyl butanol

CH3

7. CH3 CH2 O CH2 CH2 CH3 Ethoxy propane.

8. CH3 O CH2 CH2 CH2 CH3 Methoxy butane.

Note: 1, 2, 3 are positional isomers.

4, 5, 6 are chain isomers.
7 and 8 are functional isomers.

STEREO-ISOMERISM
The compounds differ by spatial arrangement of atoms. There are two types i.e.
geometrical stereoisomerism and optical stereoisomerism.

GEOMETRICAL STEROISOMERIM
Is where isomers have the same structural formula but differ in the spatial
arrangement of the groups around a double bond.

Geometrical isomers arise as a result of a double bond which is planar and does
not allow free rotation (restricted rotation) unlike a single carbon bond which
freely allows rotation.

Geometrical isomers can therefore be;

(i) Cis-geometrical isomer.
Is when identical groups of atoms are on the same plane of the double
bond.

(ii) Trans-geometrical isomer.

Is when identical atoms are rotated on opposite planes of the double bond.

But-2-ene
H CH3
C=C Trans but-2-ene.

22
CH3 H
H H
C=C Bis but-2-ene
CH3 CH3

1, 2-dichloro ethene.

H H
C = C Cis 1,2 dichloro ethene.
Cl Cl

Cl H
C=C Trans 1, 2 dichloro ethene
H Cl

Butene-1, 4-dioc acid

HOOC H

C=C Trans butane-1, 4-dioc acid.

H COOH

H H
C=C Cis butane- 1, 4-dioc acid
COOH COOH

OPTICAL ISOMERISM
Type of isomerism that arises when two or more compounds with the same
molecular or structural formula have got different optical properties in rotating
the plane of polarized light.

The optical isomers are usually not super imposable onto each other and they
have got marked differences in the physical and chemical properties.

For any optical isomers to exist, they must have a must have a mirror image of
each other and rotating a plane of polarized light either to the right or to the left.

When an isomer rotates light to the right, it is known as DEXTROROTARY

23
(D-isomer) (+ve isomer).
When it rotates light to the left, it is known as LEVOROTARY (L-isomer or –ve
isomer). E.g. lactic acid (2-hydroxy propanoic acid).

CH3 CH(OH) COOH

H3 C COOH HOOC CH3

C C
H OH HO H

D-isomer (L-isomer)

CONDITIONS OF GEOMETRICAL ISOMERS

A compound must have asymmetrical centre. This is a centre joined by four
different groups of atoms and that carbon centre is said to be asymmetric carbon.
E.g. 2-methyl butan-2-ol (amyl alcohol).
H3C OH OH CH3
C C
CH2 H H CH2 CH3
CH3
L-isomer D-isomer

Ways of writing organic compounds

(i) Using carbon-carbon bonds.
H3C – CH2 – CH2 – CH3 Butane.
H3C – CH = CH – CH2 – CH3 Pent-2-ene.

(ii) Plainly illustrating atom.

CH3 CH2 CH2 CH3 Butane.
CH3(CH2)2 CH3 Butane.

(iii) Using the molecular formula.

C4H8 Butene
C6H6 Benzene
C6H5NO2 Nitrobenzene.

24
(iv) Using skeletal structure.
(a) Pentane

(b) Hex-3-ene. Cyclohexene.

(c) 2-methyl but-2-ene Cyclohexane.

Note: No. (iv) is not commonly used at A’ level.

ORGANIC REACTIONS
Generally, most organic reactions are slow compared to inorganic reactions. At
the same time, they yield different product depending on the conditions of
reaction. When considering a particular organic reaction, conditions at which it
takes place must be specified.

TYPES OF ORGANIC REACTIONS.

There are several types of organic reactions, categorized under different ways.

Bond breaking in organic reaction.

There are two ways in which bonds can be broken in organic reactions.
(a) Heterolytic fission.
Here an organic bond is broken and the resulting electrons within a broken
bond are then taken up by one atom giving rise to ions. E.g.
Ione pair of electrons.
CH3 – Cl +CH3 + Cl-

A ÷ B A+ + B-
Ions.

(b) Homolytic fission

Type of bond breaking where by the resulting electrons in the broken bond
are equally shared by the two atoms. This results into atoms with unpaired
electrons which are called free radicals. E.g.

A ÷ B A + B
Free radicals

25
 CH3 H CH3 + H
Free radicals.

TYPES OF ORGANIC REACTIONS

1. ELECTROPHILLIC ADDITION REACTIONS

Electrophillic addition reactions are reactions in which an electrophille is
added to a reacting substrate (molecule).

An electrophille is an electron seeking species or atoms. Electrophilles are

usually positively charged. E.g. +NO3, +Cl, +CH3.

Examples:
CH2 = CH2 + Cl – Cl Cl-CH2 – CH2 – Cl.

2. ELECTROPHILLIC SUBSTITUTION REACTION.

Type of organic reaction where an electrophille is substituted by another
electrophille.
H H
H H H CH3
+ +CH3 + H+
(Electrophille)
H H H H
H H

+CH3 substitutes H+.

3. SUBSTITUTION NUCLOEPHILLIC REACTIONS

Type of organic reaction where a nucleophille replaces another
nucleophille in a reacting molecule.

A nucleophille is a species or group of atoms that seek for the positive

centre of the reacting molecule. They either be negatively charged e.g.
𝑂𝐻 , 𝐶𝑙 , 𝐵𝑟 or neutral (uncharged). E.g. H2O , NH3.
− − −

All nucleophilles must have a lone pair of electrons.

26
 CH3 CH2CH2 – Cl + OH CH3 CH2CH2 – OH + 𝐶𝑙 − .
Nucleophillic substitution reactions can either be;
(i) Substitution nucleophillic biomolecular (SN2). Here two molecules
are involved in the rate determining step of the reaction.
OR:
(ii) Substitution nucleophillic unimilecular (SN1). Here only one
molecule is involved in the rate determining step of the rnx.

4. Elimination reactions (E).

These are reactions where an atom is completely removed from the
molecule. This always results into the formation of a double or multiple
bond. E.g.
Cl
CH3 CH CH3 CH2 = CH CH3 + Cl- + H+.

NOTE: Elimination reactions can also be biomolecular (E2) or

unimolecular (E1).

FACTORS THAT AFFECT ORGANIC REACTIONS.

(i) Conditions of temperature.

Temperature affects a number of organic reactions and therefore when
writing those reactions, temperature has got to be specified.

(ii) Nature of the solvent.

The nature of the solvent used affects the type of organic reaction e.g.
aqueous condition, organic solvent condition. E.g.
𝐶𝐻3 𝐶𝐻2 − 𝐶𝑙 + 𝑂̅𝐻 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐶𝑙 −

Ethanol
CH3CH2 – Cl +∶ 𝑂̅𝐻 CH2 = CH2.
Heat

(iii) The structure of the reacting molecule.

The structure of the reacting molecule can affect the organic reaction in
several ways like.
(a) Steric hindrance.
A condition in which the surrounding alkyl groups prevent a
reagent from attaching the reaction centre e.g.

27
 CH3 CH3 CH3
H3C – C+ H 3C – C + H - C+ - H
CH3 H

Tertiary Secondary Primary

Carbocation Carbocation Carbocation

(b) Electronegativity
δ+ δ- δ+ δ+ δ-
CH3 - Cl CH3 - Br CH3 - I

(c) Bond length.

Usually longer bonds are easily broken than the shorter ones. If a
reaction proceeds by breaking a particular bond, a longer bond can
then easily be broken than a smaller one.

MECHANISM OF REACTIONS
A mechanism of an organic reaction is an illustration by showing the flow of
electrons from one centre to another. This flow is normally illustrated by means
of curled arrows.

When a double headed arrow is used, it implies two electrons are flowing i.e.
and when a single headed arrow is used, it implies one electron i.e .

The arrow must always begin at the centre of the double bond where electrons
are positioned and ends where electrons are deficient or it must begin at the
centre of a lone pair of electrons. E.g.
Electron rich

(i) CH2 = CH2 Br+ - Electron deficient centre.

(ii) Cl – Cl 2Cl

(iii) H2O

28
 +CH2 CH3 H2O+CH2CH3

ALKANES
These are saturated hydrocarbons containing carbon and hydrogen elements
only joined by a single covalent bond.

The open chain hydrocarbons (alkanes) have got a general formula of CnH2n+2
where n = a whole number.

Functional group of all alkanes is a carbon - carbon “C- C” single bond where all
the four valency electrons of carbon are involved in the bonding.

Examples:
H
n=1 CH4 H–C–H Methane
H

H H
n=2 C 2H 6 H–C–C–H Ethane
H H

H H H
n=3 C 3H 8 H – C – C – C – H Propane
H H H

NOMENCLATURE
Alkanes are named as saturated hydrocarbons by adding the suffix-ane on the
stem name of the parent hydrocarbon.

The parent hydrocarbon indicates the number of carbon atoms.

Number of carbon atoms Parent name Alkane

n=1 Meth Methane
n=2 Eth Ethane
n=3 Prop Propane
n=4 But Butane
n=5 Pent Pentane
29
n=6 Hex Hexane

The branches on the parent chain must be indicated together with their positions.

For cyclic alkanes, the word cyclo has got to be written before the parent name.
H3C CH2 CH2 CH3 n – Butane.

H3C CH2 CH CH3 2-methyl butane.

CH3

H3C – CH3 – C – H – CH2 – CH3 3-isoprophyl pentane

CH
CH3 CH3

CH2 – CH2

CH2 CH2 Cyclo pentane

CH2

ISOMERISM IN ALKANES
Alkanes exhibit structural isomerism specifically chain isomerism where the
isomers differ in the chain.

C6H14

H H H H H H
H–C–C–C–C–C–C–H n - hexane
H H H H H H

H3C CH2 CH2 CHCH3 2-methyl pentane

CH3

CH3
H3C CH2 CH CH2CH3 3-methyl pentane

30
 CH3
H3C CH CH CH3 2, 3-dimethyl butane
CH3

CH3
H3C C CH2 CH3 2, 2-dimethyl butane
CH3

PREPARATIONS OF ALKANES
1. FROM UNSATURATED HYDROCARBONS
Alkanes are prepared by reduction of unsaturated hydrocarbons e.g.
alkenes and alkynes.

When an alkene is reacted with H2, in the presence of a suitable catalyst

like nickel at 150oC, platinum (Pt) and paradium (Pd) at room temperature,
an alkane is formed. Alkynes also undergo the same reaction except that
excess H2 is required.

CH3-CH3
𝑁𝑖
CH2 = CH2 + H2
150𝑜 𝐶
Ethene Ethane

𝑃𝑡
CH3CH = CH2 + H2 CH3CH2CH3
𝑟.𝑡.𝑝
Propene Propane

H
𝑝𝑑
+ H2
𝑟.𝑡.𝑝
H
Cyclohexene Cyclohexane

CH3C≡CH + 2H2 Pt CH3CH2CH3

Propyne Propane

31
 𝑁𝑖
+ 2H2 H H
150𝑜 𝐶

Bicyclo hexa-1, 6-diene H H

Bicyclo hexane

2. FROM HALOGENO ALKANES (ALKYL HALIDES) (R-X)

(i) When alkyl halides are reduced with zinc in the presence of conc.
HCl acid, alkanes are formed.

CH3 CH2 – Cl + Zn Conc. HCl CH3CH3 + ZnCl2

Chloro ethane Ethane

Cl
+ Zn Conc. HCl + ZnCl2

Cyclo chloro hexane Cyclohexane

CH3 CH3
CH3 – C – CH3 Zn/Conc.HCl CH3 – CH – CH3 + ZnCl2.
Cl
2-chlor-2-methyl propane 2-methyl propane.

(ii) When alkyl halides are heated with sodium metal in ether (diethyl
ether) alkanes are formed but with increase in carbon chain
(doubling the carbon chain). This reaction is known as Wurtz
reaction and its usually important in organic synthesis when
doubling the carbon chain.

2CH3Br 2Na/ether CH3CH3 + 2NaBr

Bromo methane Ethane

𝑒𝑡ℎ𝑒𝑟
2CH3CH2 – Cl + 2Na CH3CH2CH2CH3 + 2NaCl
𝐻𝑒𝑎𝑡
Chloro ethane Butane

32
 𝑒𝑡ℎ𝑒𝑟
2CH3CH – CH2 – Cl + 2Na CH3CHCH2CH2CHCH3 + 2NaCl
ℎ𝑒𝑎𝑡
CH3 CH3
Chloro-3-methyl 2-methyl pentane
Propane

𝑒𝑡ℎ𝑒𝑟
2CH3CH CH2Cl + 2Na CH3CH CH2 CH2 CH CH3 + 2NaCl
ℎ𝑒𝑎𝑡
CH3 CH3 CH3
2, 5-dimethyl hexane.

2𝑁𝑎𝑙 𝑒𝑡ℎ𝑒𝑟
CH3CH2 – Cl + CH3Cl CH3CH2CH3 + 2NaCl
ℎ𝑒𝑎𝑡
n – propane
I
𝑒𝑡ℎ𝑒𝑟
+ 2Na + 2NaI
ℎ𝑒𝑎𝑡

Biphenyl

𝑒𝑡ℎ𝑒𝑟
2 CH2 – I + 2Na CH2 – CH2 + 2NaI
ℎ𝑒𝑎𝑡

1, 2 biphenyl ethane.

(iii) Reduction using zinc – copper couple.

Alky halides can be reduced using zinc-copper couple in presence of
ethanol to give alkane.

𝑍𝑛−𝐶𝑢
CH3CH2 – Cl CH3 CH3
𝐸𝑡ℎ𝑎𝑛𝑜𝑙

𝑍𝑛−𝐶𝑢
CH2 CH2 – Br CH2 CH3
𝐸𝑡ℎ𝑎𝑛𝑜𝑙

2 phenyl ethane.

33
3. FROM CARBOXYLIC ACIDS AND THEIR SALTS
Alkanes can be prepared from carboxylic acids or salts of carboxylic acids
by reacting with fused sodium hydroxide or soda lime.

(i) From carboxylic acids.

Step I:
CH3CH2COOH + NaOH CH3 CH2 CO −𝑂𝑁𝑎+ + 𝐻2 𝑂
Propanoic acid Sodium propanoate

Step II:
CH3 CH2 COO𝑁𝑎+ + NaOH(s) CH3CH3 + Na2CO3.
Ethane

Overall equation:
𝐸𝑥𝑐𝑒𝑠𝑠 2𝑁𝑎𝑂𝐻(𝑠)
CH3CH2COOH CH3CH3 + Na2CO3 + H2O.
𝐻𝑒𝑎𝑡

Note: This reaction is very important in organic synthesis by

reduction of the carbon chain length by one carbon atom.

COONa+ H
2𝑁𝑎𝑂𝐻(𝑠)
+ Na2CO3 + H2O
𝐻𝑒𝑎𝑡

Benzene

𝐸𝑥𝑐𝑒𝑠𝑠 2𝑁𝑎𝑂𝐻(𝑠)
CH3COOH CH4 + Na2CO3 + H2O
𝐻𝑒𝑎𝑡
Methane

COONa+ H
𝐸𝑥𝑐𝑒𝑠𝑠 2𝑁𝑎𝑂𝐻(𝑠)
+ Na2CO3
𝐻𝑒𝑎𝑡
COONa H
Cyclohexane

34
4. FROM CARBONYL COMPOUNDS
Reduction of carbonyl compounds using amalgamated zinc produces
alkanes in the presence of conc. HCl.

Carbonyl compounds are aldehydes and ketones containing an oxygen

atom in the carbonyl carbon, (C = O) which is removed by zinc and then
given to hydrogen to form H2O. e.g.
O
𝐻𝑔−𝑍𝑛
CH3 – C – H CH3CH3 + H2O.
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙
(Ethanal aldehyde) Ethane

O
𝐻𝑔−𝑍𝑛
CH3 – C – CH3 CH3CH2CH3 + H2O.
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙

O
𝐻𝑔−𝑍𝑛
C – CH3 CH2CH3 + H2O.
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙

35
5. CRACKING OF HIGHER ALKANES
When higher alkanes are heated under high temperatures, they break
down into shorter alkanes and sometimes alkenes are also formed.
Summary:
ALKYL HALIDE
R–X

CARBOXYLIC ACID Znl ALKYNES

R – COOH Conc. HCl R - C≡CH
(i) Excess Nal ether Excess
NaOH Heat H2
(ii) Heat Zn-Cu
Catalyst Ni
Alkane pt
R–H pd r.t.p
H2
(i) NaOH(s) (i) Hg-Zn Catalyst
(ii) HCl Nil ALKENES
(ii) Heat pt r.t.p RCH2= CH2
Pd
CARBOXYLIC CABONYL CPD
ACID SALT O
R – COONa R–C–H
O
R–C–R

Question:
Convert CH2 = CH2 to CH4.
𝑐𝑜𝑛𝑐. 𝑁𝑎𝑂𝐻(𝑎𝑞)
CH2 = CH2 + HCl CH3CH2Cl CH3CH2OH
𝐻𝑒𝑎𝑡

H2O/H+ Cr2𝑂72− /𝐻+ (𝑎𝑞)

Heat Heat

CH3CH2OH CH3COOH
𝐶𝑟2 𝑂72− (𝑎𝑞)
𝐻𝑒𝑎𝑡 𝐻+ (𝑎𝑞)
Excess
NaOH

Heat

36
 𝐸𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻(𝑠)
CH3COOH CH4 + Na2CO3
𝐻𝑒𝑎𝑡
Complete the following equations, writing the IUPAC name of the main
product.
𝐸𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻(𝑠)
1. CH3 – CH – COOH
𝐻𝑒𝑎𝑡
CH3

𝑒𝑡ℎ𝑒𝑟
2. 𝐶𝐻3 𝐶𝐻2 𝐶𝑙 + 2𝑁𝑎
ℎ𝑒𝑎𝑡

3. 𝐶𝐻3
𝑁𝑖
𝐶 = 𝐶𝐻2 + 𝐻2
150𝑜 𝐶

𝑍𝑛−𝐻𝑔
4. 𝐶𝐻3 𝐶𝐻2 − 𝐵𝑟
𝐸𝑡ℎ𝑎𝑛𝑜𝑙

Solutions:
𝐸𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻(𝑠)
1. CH3 – CH – COOH 𝐶𝐻3 𝐶𝐻2 𝐶𝐻3 + 𝑁𝑎2 𝐶𝑂3 + 𝐻2 𝑂.
𝐻𝑒𝑎𝑡
CH3 n - propane

𝑒𝑡ℎ𝑒𝑟
2. 𝐶𝐻3 𝐶𝐻2 𝐶𝑙 + 2𝑁𝑎 𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3 + 2𝑁𝑎𝐶𝑙.
ℎ𝑒𝑎𝑡
n – Butane

3. 𝐶𝐻3 𝐶𝐻3
𝑁𝑖
𝐶 = 𝐶𝐻2 + 𝐻2 𝐶𝐻 − 𝐶𝐻3
150𝑜 𝐶

2-methyl-2-phenyl ethane

𝑍𝑛−𝐻𝑔
4. 𝐶𝐻3 𝐶𝐻2 − 𝐵𝑟 𝐶𝐻3 𝐶𝐻3
𝐸𝑡ℎ𝑎𝑛𝑜𝑙
n – ethane.

37
PROPERTIES OF ALKANES
PHYSICAL PROPERTIES
(a) Nature:
Lower alkanes exist as gases (𝐶1 − 𝐶3 ) exist as gases at room temperature.
This is because they have got low boiling points.

The medium (𝐶4 − 𝐶9 ) exist as liquids. Higher alkanes are greater than 𝐶10
exist as solids at room temperature.

(b) Boiling and melting points:

Generally, the boiling points and melting points of alkanes are lower than
corresponding compounds like alcohols, carboxylic acids.

Explanation:
Alkane molecules are held by weak Vander Waal’s forces of attraction while
corresponding alcohols and carboxylic acids are held by relatively strong
hydrogen bonding.

Within alkanes, the boiling point generally increases with the increase in
molecular weight.

Ethane (30) boils at lower temperature than Butane (56).

Explanation:
Increase in the molecular weight increases the size of the molecules which
correspondingly increases the Vander Waal’s forces of attraction. That is why
butane (56) boils at a higher temperature than ethane (30).

However, when branching is considered e.g. pentane.

𝐶𝐻3
𝐶𝐻3 𝐶𝐻2 𝐶𝐻2 𝐶𝐻2 𝐶𝐻3 𝑎𝑛𝑑 𝐻3 𝐶 − 𝐶 − 𝐶𝐻3
𝐶𝐻3
mm = 72 mm = 72
(n – pentane) (2, 2-dimethyl propane)

2, 2-dimethyl propane boils at a lower temperature than n-pentane yet both are
of the same molecular weight.

38
Explanation:
2, 2-dimethyl propane is highly branched giving it a spherical shape which
reduces its size and weaker Vander Waal’s forces of attraction will exist between
the molecules. While normal pentane is a straight chain molecule which gives the
molecule, an extended structure resulting into relatively stronger Vander Waal’s
forces.

A SKETCH SHOWING BOILING POINTS OF ALKANES, ALCOHOL AND

CARBOXYLIC ACIDS
Aklanoic acid
Alkanols
Alkanes
Boiling points

Assignment:
The boiling points of alkanes with even and odd number of carbon atoms are not
the same.
(i) Identify how they differ
(ii) Explain the above difference.

COMBUSTION OF ALKANES
Alkanes usually burn in air to give 𝐶𝑂2 𝑎𝑛𝑑 𝐻2 𝑂 only and a lot of heat is
produced. This explains why alkanes are used as fuels in domestic and industrial
use. E.g. methane is an example of a bio gas that explodes readily to give heat.

Gasoline usually contains propane or butane used in domestic and industrial

heating and also to run auto-mobile.

𝐶𝐻4 + 2𝑂2(𝑔) 𝐶𝑂2(𝑔) + 2𝐻2 𝑂(𝑙) + 𝐻𝑒𝑎𝑡

𝐶3 𝐻8 + 5𝑂2(𝑔) 3𝐶𝑂2(𝑔) + 4𝐻2 𝑂(𝑙) + 𝐻𝑒𝑎𝑡

39
REACTIONS WITH HALOGENS IN PRESENCE OF (UV) LIGHT OR HEAT
Alkanes are generally unreactive but in the presence of UV radiations (like
sunlight), alkanes react with chlorine to form chloro alkane. This is an example of
a substitution reaction where 𝐻2 atoms are substituted by chlorine atoms
following a free radical mechanism.

A free radical mechanism is a type of reaction where free radicals are involved.

A free radical is a chemical species with unpaired electrons and it is always very
unstable but reactive. E.g.
Excess
𝐶𝐻4 + 4𝐶𝑙2 𝑈𝑉 𝐶𝐶𝑙4 + 4𝐻𝐶𝑙

Excess
𝐶𝐻3 𝐶𝐻3 + 𝐶𝑙2 𝑈𝑉 𝐶𝐻3 𝐶𝐶𝑙3 + 3𝐻𝐶𝑙

Limited
𝐶𝐻4 + 𝐶𝑙2 UV 𝐶𝐻3 𝐶𝑙 + 𝐻𝐶𝑙

The above reaction is a chain reaction where the products formed become the
reactants of the next step.

Therefore, the reaction can then be divided into three;

(i) Initiation step
(ii) Propagation step
(iii) Termination step

INITIATION STEP
𝐶𝐿2(𝑔) 𝑈𝑉 2𝐶𝑙

Formation of free radicals using UV. i.e.

Cl – Cl UV 2Cl
(Free radical)

40
PROPAGATION STEP
Here the free radicals generated react with neutral molecules to form new
radicals.
H
H – C – H + Cl CH3 + HCl
H

𝐶𝐻3 + 𝐶𝑙 − 𝐶𝑙 𝐶𝐻3 𝐶𝑙 + 𝐶𝑙

H
Cl – C – H + Cl CH2 + HCl
H

𝐶𝐻2 + 𝐶𝑙 − 𝐶𝑙 𝐶𝐻2 𝐶𝑙2 + 𝐶𝑙

Cl
H - C - H + Cl CH Cl2 + HCl
Cl

𝐶𝐻𝐶𝑙2 + 𝐶𝑙 − 𝐶𝑙 𝐶𝐻 𝐶𝑙3 + 𝐶𝑙

Cl
Cl – C – H + Cl - Cl 𝐶𝐶𝑙3 + 𝐻𝐶𝑙
Cl

TERMINATION
𝐶𝐶𝑙3 + 𝐶𝑙 𝐶𝐶𝑙4

𝐶𝑙 + 𝐶𝑙 𝐶𝑙2

𝐶𝐶𝑙3 + 𝐶𝐶𝑙3 𝐶𝑙3 𝐶𝐶𝐶𝑙3

41
Note: The above reaction yields a mixture of products and therefore it might be
very good in the synthesis of organic compounds. E.g. the above produces
a mixture of compounds like chloro methane, Di chloro methane, tri chloro
methane, tetra chloro methane.

However, the extent of reaction is determined by the amount of chlorine present.

NITRATION
Alkanes react with 𝐻𝑁𝑂3 acid vapour (heated 𝐻𝑁𝑂3 acid) to form Nitro alkanes,
unlike chlorination, in this reaction only one hydrogen atom is substituted by the
nitro group.
CH4 + HNO3 Heat CH3 NO2 + H2 O
Nitro methane
CH3 CH3 + HNO3 Heat CH3 CH2 NO2 + H2 O
Nitro ethane

MECHANISM

𝐻𝑂 𝑁𝑂2 𝐻𝑒𝑎𝑡 𝐻𝑂 + 𝑁𝑂2

Free radicals

H
C–C–H + OH H3C + H2O
H

𝐻3 𝐶 + 𝑁𝑂2 𝐶𝐻3 𝑁𝑂2

Petroleum industry
- How petrol is formed (distribution of petroleum)
- Cracking of alkanes (thermal cracking)
- Products of a petro – chemical industry.
- Uses of alkanes – fuels, solvents.

42
ALKENES
Alkene are unsaturated hydro carbons consisting of a carbon-carbon double
bond (- C = C -) as the functional group.

All members in alkene homologous series conform to the general formula CnH2n.

H H H H H
C=C H–C–C=C
H H H H
Ethene Propene
𝐶2 𝐻4 𝐶3 𝐻6

NOMENCLATURE
Alkenes are named as derivations of alkanes by removing the suffix “ane” and
replacing it with “ene”. E.g.
CH2 = CH2 Ethene
CH3 CH = CH2 Propene
CH3 CH CH = CH2 3 − methyl butene
CH3

CH = CH2 n − phenyl ethene

CH3
H3C – C = C – CH3
CH3 2, 3-dimethyl but-2-ene

Cyclo Hexene

CH3CH = CH CH3 but-2-ene

CH3CH2CH2CH = CH2 n – pentene

43
ISOMERISM
Alkenes exhibit four types of isomerism i.e.
(i) Chain isomerism
Examples: C4H8
CH3CH2CH = CH2 n – but-1-ene
CH3 C = CH2 2-methyl prop-l-ene
CH3

(ii) Position isomerism

These differ by the position of the double bond.
E.g. C5H10.
CH3CH2CH2CH = CH2 pent-l-ene

CH3CH = CH CH2 CH3 pent-2-ene

(iii) Ring isomerism

Isomers differ by the shape of the carbon skeleton. Alkene and clyclo-
alkanes are isomeric.
E.g. C4H8
CH3CH2CH = CH2 But ene

CH2 – CH2
H2C – CH2 Cyclo butane

C5H10
CH3CH2CH2CH = CH2 Pentene

Cyclo-pentane

(iv) Geometrical isomerism

Compounds differ by the different ways in which the atoms are arranged
by the double bond. (restricted rotation of a double bond).

Example: But-2-ene.

44
 H3 C CH3
C =C Cis but-2-ene
H H

H3 C H
C= C Tans but-2-ene
H CH3

Exercise:
Write all the isomers of C4H8
1. CH3 CH2 CH = CH2 n – but-l-ene

2. CH3 – C = CH2 2-methyl prop-l-ene

CH3

3. CH3CH = CH CH3 but-2-ene

4. CH2 CH2

H2C CH2 Cyclobutane

5. H3C H
C=C

H CH3

6. H H
C=C
H3C CH3

1 and 2 are chain isomers

3 and 4 are position isomers
5 is a ring isomer
6 is geometrical isomers

45
METHODS OF PREPARATION OF ALKENES
Alkenes are prepared from a number of ways:
(i) From Alkyl halides (Halogeno alkanes)
When halogeno alkanes are heated with an alcoholic alkaline solution like
NaOH or KOH, this reaction is an elimination reaction when both H2 and
the halogen are removed from an alkyl halide to form an alkene as a major
product and hydrogen halide as a minor product.

Conditions:
Heat
Alcoholic alkali (NaOH or KOH)

𝐴𝑙𝑐𝑜ℎ𝑜𝑙𝑖𝑐 / 𝐾𝑂𝐻
E.g. CH3CH2Cl CH2 = CH2 + HCl
ℎ𝑒𝑎𝑡
Chloro ethane

𝐶2 𝐻5 𝑂𝐻 / 𝐾𝑂𝐻
CH3CH2CH2 Br CH3CH = CH2 + H Br
𝐻𝑒𝑎𝑡
Bromo propane Propene

Cl
𝜖𝑡𝑂𝐻/𝑁𝑎𝑂𝐻
+ HCl
ℎ𝑒𝑎𝑡
Cyclo hexene

CH3
𝜖𝑡Ō/𝜖𝑡𝑂𝐻
CH3–CHCH2CH2CH2Br CH3CHCH2CH = CH2 + HBr
ℎ𝑒𝑎𝑡
CH3

(ii) Dehydration of alcohols

When alcohol is heated with conc. H2SO4 or H3PO4 acid in either liquid or
vapour phase, an alkene is formed.

Conditions:
Heat at appropriate temperature depending on the type of alcohol (170 –
180oC). Concentrated acid

E.g. Liquid phase

46
 𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2OH CH2 = CH2 + H2O
(175− 180)𝑜 𝐶
Ethene

OH
𝐶𝑜𝑛𝑐.𝐻3 𝑃𝑂4
+ H2O
𝐻𝑒𝑎𝑡

Cyclo hexanol
Cyclo hexene

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3 CH – OH CH3CH = CH2 + H2O
(170− 180)𝑜 𝐶
CH3
Propan-2-ol Propene

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH2CH2 CH CH3 CH3CH2CH = CH2 + H2O
(175−180)0 𝐶
OH
Butanol butene

VAPOUR PHASE:
When the vapour of an alcohol generated by heating, the alcohol is passed over
heated Al2O3 as a catalyst, an alkene is formed.

Aluminium
Oxide

Cotton wool
soaked in
alcohol

Potassium
Permanganate

47
Observation:
The purple solution of potassium permanganate is decolourised.

E.g.
𝐴𝑙2 𝑂3
CH3CH2OH CH2 = CH2 + H2O.
ℎ𝑒𝑎𝑡

OH
𝐴𝑙2 𝑂3
ℎ𝑒𝑎𝑡
+ H2O

CH3 CH3
3-methyl cyclo hexanol 3-methyl cyclo hexene.

The above reaction is also known as elimination reaction because an alcohol loses
a water molecule and it forms an unsaturated compound.

(iii) Dehydro Halogenations of Vicinal Dihalides

This is a reaction where there is removal of both hydrogen and halogen
atoms from one molecule to form unsaturated compound.

A Vicinal dihalide is a compound with two halogen atoms positioned at

adjacent carbon atoms. The structure is shown below.
X X
-C–C–

Vicinal is different from a Gem-dihalide.

A Gem-dihalide has got two halogen atoms positioned within the same
carbon atom. E.g.
X
- C – X Gem-dihalide

(a) When a vicinal dihalide is heated with zinc in presence of an

alcohol, an alkene is formed. E.g.
Cl
𝐶𝐻3 𝐶𝐻2 𝑂𝐻
CH3 CH = CHCH3 + Zn CH3CH = CHCH3 + ZnCl2
ℎ𝑒𝑎𝑡
Cl
2, 3-dichloro butane

48
 Cl
𝐶𝐻3 𝐶𝐻2 𝑂𝐻
+ Zn + ZnCl2.
ℎ𝑒𝑎𝑡

Cl

Br
𝑍𝑛/𝐸𝑡ℎ𝑎𝑛𝑜𝑙
CH3CH3 CH CH3 CH3CH = CHCH3 + ZnBr2
ℎ𝑒𝑎𝑡
Br

Note: Sodium metal can also be used to give the same products that atoms
of sodium are required. E.g.

Cl
𝐸𝑡ℎ𝑎𝑛𝑜𝑙
CH3CH CH2 + 2Na CH3 CH = CH2 + 2NaCl.
ℎ𝑒𝑎𝑡
Cl

(b) Using gem dihalides

Higher alkenes are produced but with an increased number of
carbon atoms and this reaction is useful in increasing the carbon
length during organic synthesis.

2CH3CHCHCl2 + 2Zn Ethanol CH3CH = CHCH3 + 2ZnCl2

2CH2Cl2 + 4Na Ethanol CH2 = CH2 + 4NaCl

(iv) Partial reduction of alkynes

When Alkynes are reacted with hydrogen in equi-molar ratio in presence
of a heated catalyst like nickel at 150oC or platinum and palladium at room
temperature, an alkene is formed.

𝑁𝑖 / 𝐻2
CH ≡ CH CH2 = CH2
150𝑜 𝐶

C≡CH CH=CH2
+ H2 pt

49
 𝑁𝑖
CH3 – CHC ≡ CH + H2 CH3 CH CH = CH2
150𝑜 𝐶
CH3 CH3

CHEMICAL REACTIONS OF ALKENES

Alkenes are generally very reactive compared to alkanes. This is so because
alkenes have a double bond consisting of 𝜋 electrons which can be easily donated
to reactants (electrophiles).

A double bond in alkenes is also shorter and stronger; that means its releases
high energy compared to a single bond.

Bond Energy KJ mol-1 Length (mm)

C–C 346 0.154
C=C 598 0.134

The above make alkenes reactive to electrophiles.

TYPES OF REACTIONS
(a) Addition reactions
Alkenes undergo addition reactions where a double bond is converted to a
single bond.
(i) Hydrogenation (Reduction)
Alkenes react with H2 in presence of heated catalyst of Nickel at
150oC or platinum and palladium of at room temperature to form
alkanes. In this reaction all the hydrogen atoms are added across a
double bond.

𝑁𝑖
CH2 = CH2 + H2 CH3CH3
150𝑜 𝐶

𝑝𝑑
+ H2
𝑟.𝑡.𝑝

Cyclo hexene Cyclo hexane

CH3 CH2 CH = CH2 + H2 Pt CH3 CH2 CH2 CH3

𝑁𝑖
+ 2H2
150

50
 This reaction forms the basis of synthesizing saturated compounds
from unsaturated e.g. formation of margarine when unsaturated fats
are heated with H2 in presence of a catalyst to form a fat
(margarine).

Determination of stability of compounds like Cis and trans-forms of

alkenes, benzene and cyclo – 1, 3, 6 – triene.

𝑁𝑖
CH3 C = C CH3 + H2(g) CH3CH2CH2CH3 + heat(28.6KJ)
150
H H

H
𝑁𝑖
CH3 C = CCH3 + H2(g) CH3CH2CH2CH3 + heat(27.6KJ)
150

The Cis form is unstable compared to the trans form.

+ 3H2(g) + heat

Mechanism:
CH2 = CH2 + 𝐻𝛿− − 𝐻𝛿− 𝑃𝑡 𝐶𝐻3 + +𝐶𝐻2 +∶ 𝐻− 𝑃𝑡
Carbon cation ion

CH3 - +CH2 CH3CH3

:H-

(ii) Halogenation
Alkenes react with halogens like Cl2, Br2, I2 in presence of an organic
solvent like carbon tetra-chloride to form a dihalide compound.

CH3 CH = CH2 + Cl2 CCl4 CH3CHCH2Cl

Cl
1,2-dichloro propane.

CH3 CH3
+ I2 CCl4 I
I
1, 2-di iodo -2-methyl cyclo hexane.

51
 CH = CH2 + Br2 CCl4 CHCH2Br
Br
1, 2 dibromo-2-phenyl ethane.

Mechanism:
CH3CH = CH2 CH3+CHCH2Cl + :Cl-

𝐶𝑙 𝛿+ − 𝐶𝑙𝛿−

CH3+CHCH2Cl CH3CH CH2Cl

:Cl- Cl

CH3 CH3
𝐼 𝛿+ − 𝐼 𝛿−
+
I

CH3 CH3
+ :I- I
I I

If the same reaction is done in the presence of H2O, then the product
formed is an hydroxyl halogeno alkane. This is because the OH
generated from water is a better nucleophile than the halogen in
addition to its presence in excess.

CH2 = CH2 H2O/Br2 HOCH2 CH2 Br

2-bromo ethanol
Mechanism

CH2 = CH2 𝐵𝑟 𝛿+ − 𝐵𝑟 𝛿− +CH2CH2Br + :Br-

H
+CH2 – CH2 Br O+ - CH2CH2Br -H+ HOCH2CH2Br + H+
H
O
H H

52
H+ + Br- HBr.

CH3 Cl2/ H2O CH3 + HCl

OH
Cl

Mechanism:
CH3
𝐶𝑙 𝛿+ − 𝐶𝑙 𝛿− CH3 + :Cl-
+
Cl

O
H H

CH3 CH3 CH3

+ O+ - H -H+ OH
Cl H Cl
Cl

H+ + Cl- HCl.

CH3CH = CH3 Br2/H2O CH3CH – CH2 + HBr.

Mechanism:
CH3CH = CH2 CH3+CH CH2 Br + Br-

𝐵𝑟 𝛿+ − 𝐵𝑟 𝛿−

CH3+CH CH2 Br CH3 CH CH2 Br -H+ CH3CHCH2 Br + H+

:OH2 O OH
H H

53
 Alternatively:
H2O + Br2 HOBr + HBr

CH3 CH = CH2 CH3+CHCH2 Br + :ŌH

Br - OH

CH3+CHCH2Br CH3CHCH2Br

:OH OH

Reactions with halogen acids (HX)

Alkenes react with halogen acids to form alkyl halides. This reaction is an
addition reaction that can proceed into two ways according to the conditions of
reaction.

(i) Electrophillic addition

This reaction occurs readily in the absence of a peroxide following an ionic
mechanism.

(ii) Free radical mechanism

This occurs in the presence of a peroxide. In both types of reaction, the
products formed are different.

CH2 = CH2 + HBr CH3CH2Br.

Bromo ethane.

CH3CH = CH2 + HBr CH3CHCH3

Br
2-bromo-propane (ionic mechanism)

𝑝𝑒𝑟𝑜𝑥𝑖𝑑𝑒
CH3CH = CH2 + HBr CH3CH2CH2Br.
(𝑅𝑂𝑂𝑅)
1-bromo propane (free radical mechanism)

54
MARKWONIKOFF RULE
Markwonikoff rule predicts the products formed when halogen acid is reacted
with unsymmetrical alkene.
The rule states that addition of an halogen acid to unsymmetrical alkene gives a
product where the hydrogen is added to the carbon atom with the lower number
of hydrogens and the halogen atom is added to the hydrogen atom across a
double bond to a carbon atom with few H2 atoms.

This reaction is followed in the absence of a peroxide. E.g.

CH3OOCH3 (peroxide) or ROOR.

In the presence of a peroxide, anti Makwonikoff’s rule applied where the

hydrogen from the halogen acid is added to the carbon atom across the double
bond with the highest hydrogen atom and the halogen goes to the carbon atom
with the least hydrogens.

Examples:
1. CH3 + HBr CH3
Br
H

Cl
2. CH3C = CHCH3 + HCl CH3 C CH2 CH3
CH3 CH3

3. CH3 CH = CH2 + HBr ROOR CH3CH2CH2Br

4. CH3 CH3
CH3 – C = CH2 + HCl ROOR CH3 CH CH2 Cl

55
MECHANISM (MARKWONIKOFF RULE)
Cl
CH3 C = CH CH3 + HCl CH3 C – CH2 CH3
CH3 CH3

CH3 C = CH CH3 H - Cl slow CH3 – C – CH2CH3 + :Cl-

CH3 CH3

:Cl- Cl

CH3 +C CH2 CH3 CH3 C - CH2 CH3

CH3 CH3

CH3 CH3
CH3 C = CH2 + HCl ROOR CH3 CH CH2Cl

MECHANISM (ANTI MARKWONIKOFF)

ROOR heat 2RO

RO + H - Cl ROH + Cl

CH3 CH3
CH3 C = CH2 + Cl CH3 C - CH2Cl

CH3 CH3
CH3 C CH2Cl + H - Cl CH3CH CH2Cl + Cl

56
The reactions follow a more stable carbo cation ions in the order of
3 > 2 > 1.

REACTIONS OF ALKENES WITH H2O IN PRESENCE OF AN

ACID(H2O/H+(aq)

MINERAL ACID WATER

When an alkene is heated with H2O in presence of H2SO4 acid, an alcohol is
formed. This reaction is known as hydration of alkenes and is used in the
preparation of alcohols.

Example:
𝐻2 𝑂/𝐻 +
1. CH3CH = CH2 CH3 CH CH3
𝑊𝑎𝑟𝑚
OH
Propane Propan-2-ol

𝐻2 𝑆𝑂4 /𝐻2 𝑂
2. OH
ℎ𝑒𝑎𝑡

Cyclo hexene Cyclo hexanol

3. CH3 OH CH3
𝐻+
CH3 C= C CH3 + H2O CH3 – C – CH CH3
ℎ𝑒𝑎𝑡
CH3 CH3
2-3-dimethyl but-2-ene 2, 3-dimethyl butan-2-ol

𝐻2 𝑂/𝐻 +
4. CH3
ℎ𝑒𝑎𝑡
CH3 OH
2-methyl cyclo hexene methyl cyclo hexan-1-ol

Mechanism:

𝐻𝛿− − 𝑂𝛿− 𝑆𝑂3 𝐻 + + ŌSO3H

+ + H OH
−𝐻+
O + 𝐻+
𝑊𝑎𝑟𝑚

57
 :OH2 H

H+ + Ō𝑆𝑂3 𝐻 𝐻2 𝑆𝑂4 .

NOTE: If the reaction is done by first reacting the alkene with the
sulphuric acid, the intermediate formed is (Alkyl hydrogen
sulphate).

𝐻2 𝑂
OSO3H OH + H2SO4.
𝐻𝑒𝑎𝑡

On diluting and warming, the product formed is the alcohol.

𝐻2 𝑂/𝐻 + (𝑎𝑞)
CH3 CH = CH2 CH3 CH CH3
ℎ𝑒𝑎𝑡
OH
Propan-2-ol

Mechanism:

CH3 CH = CH2 H+ CH3 +CH CH3

−𝐻+
CH3 +CH CH3 CH3 CH CH3 CH3 CHCH3
𝑊𝑎𝑟𝑚

:OH2 O OH
H+H

REACTIONS WITH MOLECULAR O2.

Alkenes react with molecular O2 in presence of a heated silver catalyst to form
Expoxides. Hydrolysis of expoxides with water produced diols.

2𝐴𝑔
CH3 CH = CH2 + O2 CH3 CH – CH2 + Ag2O
250𝑜 𝐶

O
Propane epoxide

CH3 CH – CH3 𝐻2 𝑂 CH3 CH CH2 OH

O OH
Propan- 1, 2-diol.

58
This reaction can also occur, when alkenes are reacted with peroxo acids. E.g.
Benzene peroxo acid.
CH3 CH = CH2 + C6H5 C – O – OH CH3 CH – CH3 +
O O Expoxides
O
C6H5 – C - OH
Benzoic acid

CH3 CH CH2 OH H2O +

OH

REACTIONS WITH OZONE (O3)

Alkenes react with ozone to form ozonides hydrolysis of ozonides in the
presence of;
NaPab H2O Na+ + Pab-

Zinc and H2O produces carbonyl compounds.

O
CH3 CH = CH2 + O3 CH3 CH CH2
O O
Propane ozonide

O O O
𝑍𝑛/𝐻2 𝑂
CH3 CH CH2 CH3 CH + HC H + ZnO
𝐻𝑒𝑎𝑡
O O Ethanol Methanal

The above reaction is very important in two main ways.

(i) In organic synthesis of converting an alkene to a carbonyl compound of
aldehyde and ketone.
(ii) It is important in the analysis of the structure of the original alkene. If one
product is formed after the hydrolysis of the ozonide, then the alkene used
is asymmetrical where the double bond is at the centre. But if two products
are formed, then the alkene is unsymmetrical.

59
 O O
𝑍𝑛/𝐻2 𝑂
CH3 CH = CH CH3 + O3 CH3 CH CH CH3 2CH3 CH + ZnO.
ℎ𝑒𝑎𝑡

O–O ethanol

CH3 CH3 O CH3

𝑍𝑛/𝐻2 𝑂
CH3 – C = CH CH3+O3 CH3 – C CH CH3 2CH3 CO +ZnO
𝐻𝑒𝑎𝑡

O O

CH3 O
CH3 C = O + CH3 CH
Propanone aldehyde
(Ketone) (Ethanal)

CH3 CH = CH2 CH3 CH – CH2

:O O: O O
O O

𝑍𝑛𝑂
HCHO + CH3 CHO CH3 CH – O – CH2
𝐻2 𝑂
O O

OXIDATION REACTION OF ALKENES

Alkenes undergo oxidation reaction using mild oxidizing agents like
Alkaline potassium permanganate to form di-ols.

During this reaction, observation made is that the purple solution mixture,
turns colourless (purple solution decolourised).

This test indicates the presence of a double bond which is converted to a

saturated compound.

Ō𝐻(𝑎𝑞)/𝑀𝑛Ō4
CH2 = CH2 HO – CH2 CH2 OH
ℎ𝑒𝑎𝑡
Ethene Ethane-1, 2-diol
60
 𝐾𝑀𝑛𝑂4 /Ō𝐻
CH3 CH = CH2 CH3 CH CH2 OH
ℎ𝑒𝑎𝑡

OH
Propane -1, 2- diol

Ō𝐻(𝑎𝑞)/𝑀𝑛Ō4
OH
ℎ𝑒𝑎𝑡
OH
Cyclo hexane-1, 2-diol.

MECHANISM:
KMnO4 K+(aq) MnŌ4(aq)

CH3 CH = CH2 CH3 – CH – CH2

O O: :ŌH O O
Mn Mn
O O O O

Inequilibrium
CH3 CH – CH2 CH3 – CH – CH2 OH + Mn𝑂42−

OH O :OH OH
:Ō
Mn
O O

61
POLYMERISATION
Alkenes undergo polymerization known as addition polymerization due to the
presence of a double bond, enabling the monomer units to repeatedly combine to
form high molecular mass products known as polymers.

During polyermerisation, a catalyst is required in order to initiate the formation

of free radicals.

Catalysts popularly used include;

(i) Molecular oxygen/peroxide
(ii) Metallic catalyst.

Example:
𝑂2 𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
1. n CH2 = CH2 𝐻𝑒𝑎𝑡 (ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝.)
( 𝐶𝐻2 − 𝐶𝐻2 ) 𝑛
𝐻𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
Ethene Polythene (Polymer)
(Monomer)

Cl
𝑂2 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
2. n CH3 C = CH3 𝐻𝑖𝑔ℎ 𝑡𝑒𝑚𝑝. C - CH2
𝐻𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑟𝑒
Cl CH3 n

𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒
3. Cl CH = CH 𝐻𝑖𝑔ℎ 𝑡𝑒𝑚𝑝. CH - CH2
𝐻𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
vinyl chloride Cl n

CH = CH2 H
𝑃𝑒𝑟𝑜𝑥𝑖𝑑𝑒
4. n C - CH2
𝐻𝑒𝑎𝑡,ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
n

Styrene Polystyrene

C - CH2
n

62
 𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
5. n CH3 CH = CH – CH = CH2 CH – CH = CH – CH2
𝐻𝑒𝑎𝑡
CH3 n
Penta-1, 3-diene Rubber

6. CH3 CH3
𝐶𝑎𝑡𝑎𝑙𝑦𝑠𝑡
CH3 C = CH – CH3 C – CH
ℎ𝑒𝑎𝑡,𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
CH3 CH3 n

7. CH3
CH2 = C – CH = CH2 CH- C = CH – CH2
CH3 n
2-methyl Buta-1, 3-diene Poly methyl Buta-1, 3-diene.
(Isoprene)

Mechanism:
ROOR Heat 2RO

RO CH2 = CH2 RO – CH2 - CH2

RO CH2 CH CH2 = CH2 RO CH2CH2CH2 CH2

RO CH2 CH2 CH2 CH2 CH2 = CH2 RO CH2 CH2 CH2 CH2 CH2 CH2

Termination:

RO CH2 CH2 ---- CH2 CH2---- CH2 CH2 OR

RO CH2 CH2 --- CH2 CH2---CH2 CH2 OR.

63
ALKYNES
Alkynes are unsaturated hydro carbons which contain a triple bond in the carbon
skeleton as their functional group.

They have a general formula CnH2n-2 where n ≥ 2.

NOMENCLATURE AND ISOMERISM OF ALKYNES

The name of alkyne is formed by replacing the end n, from the corresponding
“ane” with “yne” as shown below.

Alkyne IUPAC name:

HC ≡ CH Ethyne
CH3C ≡ CH Propyne
CH3C ≡ C CH Butyne

C ≡ CH
Phenyl ethyne.

HC ≡ CC ≡ CH Buta-1, 3- diyne.

CH3
CH3 CH C CH 3-methyl butyne

Alkynes show chain, functional and position isomerism.

PREPARATION OF ALKYNES
(a) Only ethyne can be prepared by the following methods:
(i) Partial combustion of methane, yields ethyne.
2CH4 + O2 HC ≡ CH + 4H2O.

(ii) Heating of methane in absence of air at 1500oC also yields ethyne.

CH4 1500oC C2H2

(iii) Hydrolysis of calcium carbide also yields ethyne.

CaC2 + H2O Ca (OH)2 + C2H2.

64
GENERAL METHODS FOR PREPARATION OF ALKYNES

DEHYDROHALOGENATION OF DIHALOGENATED ALKANES

This is done by using alcoholic KOH. It is an elimination reaction in which two
moles of halogen acids (HX) are lost e.g.

Cl
𝐾𝑂𝐻/𝐴𝑙𝑐𝑜ℎ𝑜𝑙
CH3 C CH3 CH3 C ≡ CH + KCl + H2O.
𝐻𝑒𝑎𝑡
Cl

Mechanism:
KOH K+ + ŌH.

CH3 CH2OH + ŌH CH3CH2 Ō + H2O.

Cl
CH3 C CH3 CH3 C = CH CH3 C ≡ CH
Cl Cl
H Ō CH2CH3 H Ō CH2CH3

TYPES OF ALKYNES
Alkynes are classified according to the position of the triple bond.
(i) Terminal
(ii) Symmetrical
(iii) Unsymmetrical

Examples:
CH3C ≡ CH Terminal/unsymmetrical
CH3CH2C ≡ CH Butyne

CH3C ≡ CCH3 Symmetrical but not terminal buta-2-yne.

CH3 C ≡ CCH2CH3 Unsymmetrical but non-terminal penta-2-yne.

CH3C ≡ CCH2C ≡ CCH3 Hepta-2, 5-diyne.

CH3 ≡ CC ≡ CH buta-1, 3-diyne.

65
PREPARATION OF ALKYNES

FROM DIHALOGENO ALKANES

When dihalogeno alkanes are heated with excess alkali in the presence of an
organic solvent like ethanol, dehydrohalogenation occurs giving an alkyne.

𝐸𝑥𝑐𝑒𝑠𝑠 𝐾𝑂𝐻
Cl CH2 CH2 Cl HC ≡ CH.
𝐸𝑡𝑂𝐻/ℎ𝑒𝑎𝑡

Convert
CH2CH2OH C ≡ CH

Phenyl ethanol Phenylethyne

CH2CH2OH CH = CH2
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
Cl2/CCl4
180𝑜 𝐶
Cl Cl
𝐸𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻
C ≡ CH CH CH2
𝐸𝑡𝑂𝐻/𝐻𝑒𝑎𝑡

Mechanism:
Cl
𝐸𝑥𝑐𝑒𝑠𝑠 𝑎𝑙𝑐ℎ𝑜𝑙𝑖𝑐
CH3- CH - CH2Cl CH3C ≡ CH
𝑁𝑎𝑂𝐻/𝐻𝑒𝑎𝑡

NaOH + EtOH ⇌ EtŌNa+ + H2O

EtŌNa+ EtŌ: + Na+.

Cl Cl H
CH3 C - CH2 Cl CH3 – C = C CH3 C ≡ CH
H H

EtŌ: EtŌ:

66
(ii) From CaO.
This method is specifically for ethyne.
𝐻𝑒𝑎𝑡
CaO(s) + 3C(s) 𝑜
CaC2 + CO(g)
2000 𝐶

CaC2(s) + 2H2O(s) HC≡ CH + Ca(OH)2

Convert C(s) CH3 CH2 OH

+
CaO
2000oC Heat 𝐻+ (𝑎𝑞)/𝐻2 𝑂

CaC2 CH2 = CH2

2H2O Limited H2

HC ≡ CH Ni/150oC

(iii) From alkane (CH ≡ CH)

Partial oxidation of alkanes.
CH4 + ½ O2 HC ≡ CH + H2O
2CH4 CH ≡ CH + 3H2
1500oC
Thermal
cracking

REACTIONS OF ALKYNES
(i) Electrophilic addition
Is where an electron seeking species is added across a triple bond. Alkynes
are very reactive because of the presence of 𝜋 electrons in a triple bond.
This reaction is essentially like that of alkenes, however, 2moles of the
electrophile are required to saturate an alkyne.

(ii) Addition of halogen (X2)

CH ≡ CH + Cl2 CCl4 ClCH = CHCl
Cl2/CCl4
Cl2CH – CHCl2

67
 Overall
CH ≡ CH + 2Cl2 CCl4 Cl2CHCHCl2
1, 1, 2, 2 tetrachloro ethane.

Mechanism:
Cl
CH ≡ CH Cl - Cl H C = +CH + :Cl-

Cl Cl
H C = CH H – C = CH
+ Cl

:Cl-

Cl Cl Cl

H C = CH Cl - Cl H C – +CH + :Cl-
Cl Cl

Cl Cl Cl Cl
H C – +CH H C - CH
Cl Cl Cl

:Cl-

Br
CH3 C CH + 2Br2 CCl4 CH3 C CH Br
Br Br

(iii) Halogen acids (HX)

Alkynes react with halogen acids to give dihalides depending on the
structure of an alkyne, the dihalide can either be a gem or vicinal due to
Makwonikoff’s rule.

68
CH ≡ CH + 2Br CH3CHBr2
Cl Gem dihalides
CH3C ≡ CH + 2HCl CH3 C CH3
Cl

CH3C ≡ CH + 2HBr ROOR CH3 CH2 CH Br.

C ≡ CH + 2HBr Br
C CH3
Br

(iv) With H2O.

Alkynes react with H2O in the presence of H2SO4 acid and HgSO4
with a temperature of about 60oC to form carbonyl compounds. A
symmetrical alkyne forms a ketone.

𝐻2 𝑆𝑂4 /𝐻𝑔𝑆𝑂4
CH3C≡ CCH3 + H2O O
60𝑜 𝐶
CH3 C CH2 CH3
Butan-2-one

𝐻2 𝑆𝑂4 /𝐻𝑔𝑆𝑂4
CH3C ≡ CH + H2O CH3CH2CHO
60𝑜 𝐶,𝑅𝑂𝑂𝑅
Propanal

(v) Reactions with H2.

Alkynes just like alkenes react with H2 when passed over a suitable
catalyst like Ni/150oC, pt/r.t.p to form an alkane.
𝑁𝑖
CH ≡ CH + 2H2 CH3CH3
150𝑜 𝐶
𝑝𝑡
CH3C ≡ CH + 2H2 CH3CH2CH2
𝑟.𝑡.𝑝

(vi) Nitrile formation

When little NH3 is passed over an alkyne heater over an Al catalyst
at 573oC, a nitrile is formed.

𝐴𝑙(𝑠)
CH ≡ CH + NH3 CH3 CN + H2
573𝑜 𝐶
Ethanonitrile

69
 (vii) Polymerisation
Due to the presence of a triple bond, alkynes polymerise to form
cyclic or aromatic compounds. This occurs when an alkyne is heated
in a glass tube containing Fe catalyst (4000oC).

𝐹𝑒
3CH ≡ CH
4000𝑜 𝐶

When two molecules of ethyne combine by passing them through a

saturated solution of copper(I) chloride in ammonium chloride,
vinyl ethyne is formed.

Vinyl ethyne is a good starting material for linear polymers.

𝐶𝑢𝐶𝑙
2CH ≡ CH CH2 = CHC ≡ CH
𝑁𝐻4 𝐶𝑙
Vinyl ethyne.

CH2 = CHC ≡ CH + CH ≡ CH

CH2 = CH CH = CHC ≡ CH

A terminal proton of an alkyne can be substituted by other electropositive

metals. This indicates that, such alkynes are acidic.

NOTE: Only terminal alkynes behave this way. Non-terminal do not.

CH CH + 2Na Liquid NH3 + ̅

𝑁𝑎𝐶 ≡ 𝐶̅ Na+ + H2.

2CH3C ≡ CH + 2Na Liquid NH3 2CH3C ≡ 𝐶̅ 𝑁𝑎+ + H2.

WITH AMMONIACAL COPPER(I) CHLORIDE SOLUTION

Similary, H2 in alkynes can be substituted when it’s passed in solution of CuCl in
NH3 giving a red precipitate of Cu+ alkyne derivative. This reagent is called
ammoniacal copper(I) chloride solution, CuCl/NH3(aq).

HC ≡ CH + CuCl 𝑁𝐻3(𝑎𝑞) CuC ≡C Cu + 2HCl.

Red ppt.
Copper(I) ethyne (or Copper acetylide)

70
WITH AMMONIACAL SILVER NITRATE SOLUTION.
When a terminal alkyne is bubbled through a solution of ammoniacal AgNO3, a
white precipitate of silver dicarbide is formed.

HC≡ CH + 2 AgNO3 + 2NH3(aq) Ag C ≡ C Ag(s)

White ppt + 2NH4NO3.

Differentiate between CH3 C ≡ CH and CH3 C ≡ CCH3

Reagent: Ammoniacal copper(I) chloride solution.

With CH3C ≡ CH : No observable change.
With CH3C ≡ CCH3 : A red precipitate is observed.

The above reactions are used for distinguishing between terminal alkynes and
non-terminal

SYNTHESIS OF HIGHER ALKYNES

When an alkyne is passed through liquid NH3 in presence of Na metal and the
derivative formed is reacted with an alkyl halide, the chain is increased giving a
higher alkyne.

HC ≡ CH + 2Na Liquid NH3 𝑁𝑎+ 𝑐 − ≡ 𝐶̅ Na+ + 2CH3Cl

CH3C ≡ C CH3 + 2NaCl

CH3C CH + Na 𝑁𝑎𝑁𝐻2 CH3C ≡ 𝐶̅ 𝑁𝑎+

CH3C ≡ 𝐶̅ N𝑎+ + CH3CH2Cl CH3 C ≡ CCH2 CH2 + NaCl

Physical properties of alkynes

• They are insoluble in H2O.
• They are very soluble in organic solvents like benzene, CCl4.
• They are less dense than H2O.
• Their boiling points increase in number of carbon atoms. E.g. Ethyne boils at
-75, propane -43, butyne at 91.
• They have got almost the same boiling points as those of corresponding
alkenes.
• They have got the same vanderwaal’s forces of attraction.

71
Convert CH ≡ CH CH3

CH3 CH3

2CH ≡ CH + Na 𝑁𝑎𝑁𝐻2 2CH ≡ 𝐶̅ 𝑁𝑎+ + H2

CH ≡ 𝐶̅ 𝑁𝑎+ + CH3Cl CH ≡ CCH3

𝐹𝑒
3CH3C ≡ CH CH3 CH3
400𝑜 𝐶

CH3

72
 AROMATIC COMPOUNDS (ARENES)

The term aromatic is derived from the Greek work Aroma to mean sweet smell.
This term has been carried forward by modern Chemists used as aromatic to
mean or describe the study of compounds with benzene ring.
Benzene is a parent compound of aromatic compounds.

STRUCTURE AND BONDING OF BENZENE

Structure and bonding of benzene was made clear by analysis made by
Chemists. They found out that a clear colourless compound was isolated from
distillation of crude oil and on analysis, it was found to contain 92.3% carbon and
7.7% hydrogen only.
When 0.250g of this liquid was vapourized at 100oC, they found out that the
liquid occupies 98cm3. The results were subjected to analysis.

Element C H
Percentage composition 92.3 7.7
92.3 7.7
Relative atoms
12 1

Moles 7.69 7.70

7.69 7.70
Mole ratio
7.69 7.69

1 1
Empirical formula = CH

Volume of gas at 100(373) K

24 𝑥 373
=
293

= 30.04 dm3

98cm3 of liquid contain 0.25g at 100oC.

6.25 𝑥 30040
Mass of 1mol ( )𝑔
98
= 76.6 ≏ 77g.

(CH)n = 77
12n + n = 77

73
 77
n=
13
n = 5.0 ≏ 6.

Molecular formula is C6H6.

The structure proposed was C6H6 with all its isomers.

In 1865, Kekule proposed that the structure of benzene molecule is not a straight
chain but an hexagonal ring consisting of alternating double bonds.

H H
C C
H H OR H H
C C C C

C C H C C H
H H
C C
H H

But a number of evidences proved out that the above structure, proposed by
Kekule was not true. Benzene does not have true double bonds since it does not
undergo addition reaction with bromine in darkness.

EVIDENCE PUT TO EXPLAIN BENZENE STRUCTURE.

(i) X-ray structure determination to measure the length of carbon-carbon
bonds.

Compound Bond Length/nm

Cyclo hexane C–C 0.154
Cyclo hexene C=C 0.134
Benzene C C 0.140

The measurements of the bond length showed that, the bond length of benzene
are between single and double, therefore are not true double bonds ruling out
Kekule’s structure of double bonds.
(ii) Thermodynamic measurements:
(a) Enthalpy of hydrogenation.

74
 𝑁𝑖
+ H2 ΔH = -119 KJ mol-1.
150𝑜 𝐶

Cyclo hexene Cyclo hexane

𝑁𝑖
+ 3H2 ΔH = 3(119)
150𝑜 𝐶
Cyclo hex-1, 3, Cyclo hexane -357 KJ mol-1.
5-triene

+ 3H2 ΔH = -207 KJ mol-1.

Benzene

Conclusion:
The double bonds of benzene are not true double bonds.
Benzene is more stable than cyclo hex-1, 3, 5, triene by an extra 150 KJmol-1

(b) Enthalpy of formation of benzene.

The theoretical/calculated enthalpy of formation of benzene is 252
KJ mol-1 but the practical value of this energy is 82 KJ mol-1. This
means benzene is more stable by 170 KJ mol-1 of energy.

6C(s) + 3H2(g) C6H6(g) ΔH = 82 KJ mol-1.

(c) Reactions of benzene

Benzene does not undergo addition reactions but undergoes
substitution reactions implying it does not have double bonds but a
system of delocalized electrons or the pie (𝜋 system).

DELOCALIZATION OF BENZENE STRUCTURE

75
 H
C Delocalized electron
H–C C–H

C C–H
H
C
H
Benzene structure has got six 𝛿 carbon – carbon bonds.
It has got 3-𝜋 carbon – carbon bonds.
The 𝜋 bonds are not localized but they are shared by the six carbon atoms giving
a 𝜋 system of electrons and this is called delocalization.

STRUCTURE OF BENZENE.

Or Or Or

I II III IV

BENZENE
Is the parent aromatic compound with a hexagonal ring of carbon atoms having
a 𝜋 system of electrons.

FORMATION OF BENZENE
(i) From dehydrogenation of cyclo hexane when heated with Pt/Pd or heated
with Sulphur. Cyclo hexane loses H2 atoms to form benzene.

𝑃𝑡/𝑃𝑑
+ 3H2
ℎ𝑒𝑎𝑡

𝑆
+ 3H2S
ℎ𝑒𝑎𝑡

(ii) Polymerization of ethyne

When ethyne is heated with an organo iron or Nickel, it undergoes
cyclisation to form benzene.

𝐹𝑒
3CH ≡ CH
ℎ𝑒𝑎𝑡

76
 𝑂𝑟𝑔𝑎𝑛𝑜−𝑁𝑖
3CH ≡ CH
ℎ𝑒𝑎𝑡

(iii) Decarboxylation of benzoic acid

When benzoic acid is heated with soda lime (a mixture of (NaOH and
CaO).
COOH
𝐸𝑥𝑐𝑒𝑠𝑠 𝑠𝑜𝑑𝑎 𝑙𝑖𝑚𝑒
(𝑁𝑎𝑂𝐻)ℎ𝑒𝑎𝑡
+ Na2CO3.
Two step reaction

COOH + NaOH Heat COONa + H2O.

COONa + NaOH Heat + Na2CO3.

(iv) From benzene diazonium SaH.

When benzene diazonium salt is reacted with pypophosphorus acid in
presence of water, benzene is formed.

The formation of benzene diazonium alt can be started from phenyl amine
which is reacted with a mixture of NaNO2 and HCl (HNO2 acid) at a
temperature <10.
NH2 𝑁2+ 𝐶𝑙
𝑁𝑎𝑁𝑂2 /𝐶𝑜𝑛𝑐.𝐻𝐶𝑙
<10𝑜 𝐶
Benzene diazonium salt.

NH2 𝑁 + ≡ 𝑁𝐶𝑙 −
𝑁𝑎𝑁𝑂2 /𝐶𝑜𝑛𝑐.𝐻𝐶𝑙
<10𝑜 𝐶
Benzene diazonimu
chloride salt.

H2O H3PO2 C6H5N2Cl

Benzene.

77
(v) Catalytic reformation of petroleum under heat of about 550oC in the
presence of Cr2O3/Al2O3.

𝐶𝑟2 𝑂3
CH3(CH2)4 CH3 + 4H2
550𝑜 𝐶
Hexane Benzene

(vi) From phenol

When phenol is heated with zinc dust, benzene is formed.

OH
+ Zn heat + ZnO
Phenol

PROPERTIES OF BENZENE
PHYSICAL PROPERTIES
✓ It is a colourless liquid.
✓ It has got a x-tic smell.
✓ It is insoluble in water but dissolves in organic solvents e.g. CCl4, methyl
benzene.
✓ It burns with a highly sooty flame.

CHEMICAL PROPERTIES
Benzene undergoes Electrophillic substitution reaction where the hydrogen atom
on the ring is replaced by another electrophille. Benzene therefore reacts mainly
with Electrophilles (Positively charged species) to form substituted products on
the benzene ring.

(i) Nitration reaction

Is a reaction where the nitronium ion +NO2, O = +N = O) substitutes the
hydrogen in the benzene ring. The electrophille of the nitronium ion is
generated from a mixture of Conc. H2SO4 and Conc. HNO3 acid heated at a
temp. of 60oC.
NO2
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
+ H+
ℎ𝑒𝑎𝑡/60𝑜 𝐶
Nitro benzene

78
 Mechanism:
H2SO4 + OH – NO2 Protonation H2O+ = NO2 + HS𝑂4−

H2O+ NO2 H 2O + +
𝑁𝑂2

NO2 NO2
O= +
𝑁= O H + H+

OR: NO2 NO2.

+NO2 H -H+

(ii) Sulphonation:
This is a reaction where benzene reacts with Conc. Or fuming H2SO4 acid
to form benzene sulphuric acid.

The electrophille in this reaction is SO3 which is a neutral electrophille

generated from fuming sulphuric acid.

Fuming H2SO4 SO3H

Mechanism:
2H2SO4 SO3 + H3O+ + HS𝑂4−

O O O S 𝑂− S𝑂3− + 𝐻+
S
H
O Benzene Sulphonic acid

SO3H

79
(iii) Halogenations
Benzene reacts with halogens like Cl2, Br2 only in the presence of halogen
carrier which polarizes the halogen molecule by accepting the lone pair of
electrons so that the eletrophille is generated.
In the absence of the halogen carrier, benzene does not react with halogens.
Examples of halogen carries used are:
Al Cl3 CH3COOH
FeCl3
BF3 Fe, Cl2/Heat

+ Cl2 Al Cl3 Cl + HCl

+ Br2 Fe Br3 Br + HBr

3𝐼2 /𝐹𝑒
I + HI
𝐻𝑒𝑎𝑡

Mechanism:

𝐹𝑒(𝑠)
+ Cl2 Cl
ℎ𝑒𝑎𝑡

Mechanism:
3Cl2(s) + 2Fe(s) heat 2FeCl3

𝐶𝑙 𝛿+ − 𝐶𝑙 𝛿− − − − 𝐹𝑒𝐶𝑙3 [𝐹𝑒𝐶𝑙4 ]− 𝐶𝑙 +

Cl
+
𝐶𝑙 [𝐹𝑒𝐶𝑙4 ] −
𝐻 + 𝐹𝑒𝐶𝑙4−

Cl

+ H+

Fe𝐶𝑙4− + 𝐻+ 𝐹𝑒𝐶𝑙3 + 𝐻𝐶𝑙

Alkylation of Benzene
80
This is the reaction where an aromatic compound reacts with an alkyl halide in
the presence of a halogen carrier to form an alkyl aromatic compound.
This reaction was first identified by Friedel craft. It is also called Friedel Craft
alkylation.

+ CH3Cl AlCl3 CH3 + HCl

Chloro methane
Methyl benzene (Toulene)

+ CH3CH2Br AlBr3 CH2CH3 + HBr.

Bromo ethane Ethyl benzene

+ (CH3)3 C - Cl FeCl3 C – (CH3)3 + HCl

Mechanism
CH3 CH3
CH3 - C - Cl ------- Fe Cl3 H3C – C+ (Fe𝐶𝑙4 )−
CH3 CH3

CH3 C(CH3)3
+C – CH3(Fe𝐶𝑙4 )− H + (Fe𝐶𝑙4 )−

CH3
C – (CH3)3

+ H +.

𝐹𝑒𝐶𝑙4− + 𝐻 + FeCl3 + HCl.

+ CH3CH2CH2Br FeBr3 CH – (CH3)2 + HBr.

Mechanism:
CH3CH2CH2 Br…………FeBr3 CH3 CH2 +CH2 +(FeBr4)-

81
 Re-arrangement.
CH3 +CHCH3 (FeBr4)-

CH3 CH(CH3)2
+CH (FeBr4)- H + FeB𝑟4−
CH3

CH(CH3)2 + H+

H+ + FeB𝑟4− Fe Br3 + HBr.

+ CH2 = CH2 H+ CH2 CH3.

Benzene reacts with alkenes in presence of a mineral acid.

The mineral acid is necessary to form an electrophille.

CH3 H3C – CH – CH3

𝐻2 𝑃𝑜4(𝑎𝑞)
+ CH3 CH = CH2 CH Or
CH3

Mechanism:
CH3CH = CH2 + H+ CH3 +CH CH3

+CH(CH3)2 CH – (CH3)2
1

𝐴𝑙𝐶𝑙3
+ CH3CH = CH2 + HCl
95𝑜 𝐶

82
Acylation
Is a reaction of benzene with acid halides in the presence of halogen carriers to
form aromatic ketones at a temperature of 50oC.

1. O
𝐴𝑙 𝐶𝑙3
+ CH3COCl C CH3 + HCl
50𝑜 𝐶
Ethanol/
Chloride Phenyl ethanone

O O
𝐴𝑙 𝐶𝑙3
2. + C Cl C + HCl
50𝑜 𝐶

Mechanism:
O O
CH3 𝐶 𝛿+ − 𝐶𝑙 𝛿− − −𝐴𝑙𝐶𝑙3 𝐶𝐻3 𝐶 + (𝐴𝑙𝐶𝑙4 )−

O O
+C (𝐴𝑙𝐶𝑙 )− C – CH3 + 𝐴𝑙 𝐶𝑙4−
4
CH3 H

COCH3 + H+.

𝐴𝑙 𝐶𝑙4− + H+ Al Cl3 + HCl.

Hydrogenation:
Benzene react with hydrogen in presence of Ni catalyst when heated at 150oC to
form cyclo hexane.

𝑁𝑖
+ H2
150𝑜 𝐶

83
Halogen in presence of light (uv).
When chlorine is mixed with benzene in the presence of sun light or uv rays, the
benzene ring becomes highly substituted with chlorine atoms to form 1, 2, 3, 4, 5,
6 hexa chloro benzene.

Cl
+ 3Cl2 UV Cl Cl

Cl Cl
Cl
1, 2, 3, 4, 5, 6 – hexa chloro
Cyclo hexane.

Combustion
Benzene burns in air with a sooty flame to form CO2 and H2O.

1
+ 𝑂2(𝑔) 6𝐶𝑂2(𝑔) + 3𝐻2 𝑂(𝑙) .
2

DERIVATIVES OF BENZENE

CH3 NO2 SO3H

Methyl Nitro Benzene

Benzene Benzene Sulphuric acid

COOH Br

Benzoic Bromo benzene

acid
Cl
OH NH2
Chloro benzene
(Phenol) (Phenyl amine)

84
Derivatives of benzene react differently depending on the behaviour of the group
of atoms(s). the chemical behaviour of these groups are divided into three
groups.
(i) The group which substitutes the benzene ring directing any incoming
group 2(ortho) and 4(para) position directors. E.g.
(a) OH-group, ethoxide group OCH3, CH3-gp, NH2-nitro group, amide
group
O
-HN- C CH3.
These groups have got positive inductive effect by pushing the
electrons towards the ring, activating the benzene ring so that the
electrons are available at positions 2, 4, and 6 where the incoming
electrophille are added.

By activating the ring, they increase the electron density on the ring
so that the Electrophilles are added faster.

Usually two products are given, i.e. position 2 and position 4

products.

METHYL BENZENE
1. CH3 CH3 CH3
𝐻𝑁𝑂3 /𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
(𝐹𝑎𝑠𝑡𝑒𝑟)< 60𝑜 𝐶
2 nitromethyl
Benzene NO2
4-nitromethyl
Benzene
HNO3 + H2SO4 H2O+ - NO2 + HS𝑂4−

H2𝑂± NO2 H2O + +

𝑁𝑂2

CH3 CH3 CH3

+
𝑁𝑂2
+ H + +
H NO2
(transitional state)
H3C

NO2

85
2. NH2 NH2 NH2
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
NO2 +
𝐻𝑒𝑎𝑡
2-nitro
NO2 4-nitro.

3. OCH3 OCH3 OCH3

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
NO2 +
𝐻𝑒𝑎𝑡
2-nitro
NO2 4-nitro

Alkylation of methyl benzene.

CH3 CH3 + CH3
+ CH3Cl 𝐴𝑙 𝐶𝑙3 CH3

CH3

(a) Halogation of methyl benzene.

CH3 CH3 CH3
𝐴𝑙 𝐶𝑙3
+ Cl2 𝑜
Cl +
40 𝐶

Cl

(b) Halogenation of methyl benzene in presence of sunlight (UV).

CH3 CH2Cl
+ Limited UV + HCl
Cl2
Excess Phenyl chloro methane
Uv Cl2

C Cl3
+ 2HCl.

This reaction follows a free radical mechanism.

86
 CHLORO BENZENE
Cl

Chloro benzene or other halogeno benzene compounds can substitute the ring at
position 2 and 4 but at a much slower rate. This is because halogens have got a
negative inductive effect (electronegative) and withdrawal electrons from the
ring towards themselves so that the pie electrons on the ring can be availed to
Electrophilles at position 2 or 4 where there is a high electron density.

Cl Cl Cl
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
+ NO2 +
ℎ𝑒𝑎𝑡

NO2

Cl Cl Cl
𝐴𝑙 𝐶𝑙3
+ CH3Cl CH3
40𝑜 𝐶

CH3

Groups that direct further substitution at position 3 of the ring do so at a much

slower rate including COOH, NO2, CN, SO3H.

BENZOIC ACID
COOH
Meta (3) position directors.

Carboxylic acid on benzoic acid directs the incoming substituents at position 3 so

that one major product is formed.

(i) COOH COOH

𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3 /𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
𝐻𝑒𝑎𝑡
NO2
3-nitro benzoic acid.

(ii) COOH COOH

87
 𝐶𝐻3 𝐶𝑙
𝐴𝑙 𝐶𝑙3 /ℎ𝑒𝑎𝑡
CH3
(iii) Sulphonating
COOH COOH
𝑓𝑢𝑚𝑖𝑛𝑔 𝐻2 𝑆𝑂4

SO3H

(iv) NO2 NO2

𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3 /𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
𝐻𝑒𝑎𝑡
NO2

The above are Meta (3) directors because they pull electrons away from the ring
and decreasing electron density at position 2 or 4 and the only place where the
electrons are available is the Meta position.

DISTRIBUTED COMPOUNDS
When there are two substituents on the benzene ring, the orientation effect of
these two will be determined or predicted by their reinforcing effects or the order
of their superiority. The following order is normally observed.

- OR > NR2 > Alkyl group > halogen > Meta directors.

CH3 CH3
𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3 /𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
NO2
𝐻𝑒𝑎𝑡

NO2 NO2

COOH COOH
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3
ℎ𝑒𝑎𝑡
SO3H NO2 SO3H

CH3 CH3
𝐶𝑜𝑛𝑐.𝐻𝑁𝑂3 /𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
NO2
𝐻𝑒𝑎𝑡

Cl Cl

88
COOH COOH
Br 𝐶𝑙2 𝐴𝑙 𝐶𝑙3 Br +

Cl

Cl Cl
𝑓𝑢𝑚𝑖𝑛𝑔 𝐻2 𝑆𝑂4 +

Cl HSO3 Cl

𝐶𝑙2 /𝐴𝑙𝐶𝑙3 +
diphenyl Cl

89
 ALKYL HALIDES
(Halogeno alkanes)

Alkyl halides are compounds in which halogen atoms are directly attached onto
the hydro carbon chain or aromatic ring.

R – X where R = Alkyl or Aryl group.

X = Halogen atom (Cl, Br, I, F)

When the halogen is attached to the aromatic ring, it is called aromatic halide.
e.g.
Cl I Br.

When the halogen is directly attached to the hydro carbon, it is called alkyl
halide / halogen alkane. E.g.
CH3CH2Cl, CH3Br, CH3CHCH3
Chloro ethane Bromo methane I 2-Iodo propane.

ALKYL OR HALOGENO ALKANES

Nomenclature:
Alkyl halides are named as derivatives of corresponding alkanes y inserting the
number and the prefix, chloro, Bromo, Iodo, Fluoro, to the alkane name.

Example:
CH3Cl Chloro methane
CH3CH2Br Bromo ethane
CH3CHCH3 2-Iodo propane.
I
CH3 Cl
CH3 CH CHCH3 2-chloro-3-methyl butane.

CH3
CH3 – C – Br 2-Bromo, 2-methyl propane.
CH3

90
ISOMERISM
Alkyl halides exhibit two types of isomerism.
(i) Chain isomerism
(ii) Positional isomerism

CHAIN ISOMERISM:
These arise as a result of difference in the arrangement of carbon atoms giving
different carbon skeleton but the position of the halogen atom remains the same.
C4 H9 Br.

1. CH3 CH2 CH2 CH2 Br 1-Bromo butane.

2. CH3 CH CH2 Br 1-Boromo-2-methyl propane.

CH3

POSITIONAL ISOMERISM:
These arise as a result of the different positions taken by the halogen atom on the
same chain. E.g.
C4 H9 Br.

CH3 CH2 CH2 CH2 Br 1-Bromo butane

CH3 CH2 CH CH3 2-Brobom butane

Br

METHODS OF PREPARATION:
Alkyl halides are prepared from the following:
(i) From Alkenes:
Addition of a halogen acid to an alkene at room temperature gives an alkyl
halide. When unsymmetrical alkene is used, addition of a halogen acid
gives a product predicted by Makwonikoff’s rule. But if a peroxide used,
then the product will be that of anti Makwonikoff’s rule.
Br
1. CH3CH = CH2 + HBr r.t.p CH3 CH CH3

𝑅𝑂𝑂𝑅
2. CH3 CH = CH2 + HBr CH3 CH2CH2 Br.
𝐻𝑒𝑎𝑡

91
3. CH = CH2 Cl
+ HCl CH CH3

4. + HI I
Iodo cyclo hexane.

5. CH3 CH3
C = CH2 + HCl C – CH3
Cl

Mechanism:
CH3 CH3

C = CH2 𝐻𝛿+ − 𝐶𝑙 𝛿− slow +C - CH3 + Cl-

CH3 CH3
+C – CH3 fast C – CH3
Cl- Cl

(ii) From Alkanes

When alkanes are reacted with a halogen molecule in presence of UV rays
of sunlight. A mixture of alkyl halides are formed but if the reaction
conditions are controlled by using excess alkane or limited halogen
molecule, then the product formed would be one type of alkyl halide.

Excess:
𝑈.𝑉
CH3 CH2 CH3 + Cl2 CH3CH2CH2Cl + HCl.
𝑆𝑢𝑛𝑙𝑖𝑔ℎ𝑡

limited
CH3 + Cl2 UV CH2Cl + HCl.

92
(iii) From Alcohols:
Alcohols are the most important source of preparing alkly halides in
reaction where hydroxyl groups of alcohol are replaced by halogen atoms
which could be derived from: - halogen acids (HX).
▪ Phosphorus tri or penta halides
(PX3/PX5)
▪ Thiony chloride (SOCl2).

(a) Action of halogen acid on the alcohol:

When a halogen acid is heated with an alcohol in presence of a
dehydrating agent e.g. - Zn Cl2 (anhydrous)
- Conc. H2SO4.
- Al2O3 (Dry)
An alkyl halide is formed. Sometime the halogen acid is generated
“insitu.”

R – OH + HX R – X + H2O.

CH3 CH2 OH NaCl/Conc.H2SO4 CH3CH2 – Cl + H2O.

anhydrous
CH3 CH CH3 + H + HCl ZnCl2 CH3 CH CH3 + H2O
OH Cl

CH3 CH3
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙
CH3 – C – OH CH3 – C – Cl + H2O
𝐴𝑛ℎ𝑦𝑑𝑟𝑜𝑢𝑠 𝑍𝑛 𝐶𝑙2
CH3 CH3

A solution of anhydrous ZnCl2 in Conc. HCl (Lucas reagent) is an

important reagent for distinguishing the three classes of alcohols i.e.
- Primary.
- Secondary and tertiary alcohols.
The tertiary alcohol gives an immediate cloudy solution of an alkyl
halide. (0.5 minutes).
The secondary alcohol gives cloudy solution between 5 and 10
minutes.
The primary alcohol does not give a cloudy solution at room
temperature.

93
(b) Action of phosphorous halides:
When alcohols are refluxed with phosphorous halide like
phosphorous tri chloride or phosphorous Pentachloride, the
halogeno alkanes or alkyl halides are formed.

R – OH + PCl5 refluxed R – Cl + POCl3 + HCl.

CH3 CH2 OH + PCl5 refluxed CH3 CH2 Cl + POCl3 + HCl

𝑃𝐶𝑙5
CH2OH CH2 Cl + POCl3 + HCl.
𝑅𝑒𝑓𝑙𝑢𝑥𝑒𝑑

3CH3 CH2 OH + PCl3 reflux 3CH3 CH2 Cl + H3PO3.

(c) Action of thionyl chloride (SOCl2):

When alcohols are refluxed in presence of thionyl chloride in the
presence of an organic base pyridine to neutralize the mixture of
toxic gases, an alklyl halide is formed.

This is a very convenient way of preparing alkyl halides.

𝑝𝑦𝑟𝑖𝑑𝑖𝑛𝑒
CH3CH2OH + SOCl2 CH3 CH2 Cl + SO2 + HCl
ℎ𝑒𝑎𝑡

CH2 OH + SO Cl2 pyridine CH2 Cl + SO2 + HCl.

94
 REACTIONS OF ALKYL HALIDES

CLASSES OF HALOGENO ALKANES

(i) Primary Alkyl halides RCH2 CH2 – X.
Here the halogen atom is attached to a carbon is which bonded to only one
another.

(ii) Secondary alkly halide. R – CH – R2

X
Here the halogen atom is attached to a carbon atom which is bonded to
two other carbon atoms.

(iii) Tertiary alkly halide: R1

R2 – C – X
R3
Here the halogen atom is attached to a carbon atom which is bonded to
three other carbon atoms.

The three classes of alkyl halides given above react differently due to the
stability of the carbo cation ion which is formed as an intermediate during
the reaction. The stability is governed by the order that tertiary >
secondary > primary.

R1 R1 H
R2 – C + H – C+ R1 – C – C
R3 R2 H
Tertiary Secondary Primary

PHYSICAL PROPERTIES:
Lower alkyl halides are gases at room temperature.
The medium ones are liquids and the higher ones are solids.
The boiling points of alkyl halides with the same number of carbon atoms is
determined by the atomic size of the halogen which later is as a result of the Van
de Waal’s forces of attraction.

I- > Br- > Cl- > F-.

95
 CH3 CH3 CH3
H3C – C – I H3C – C – Br H3C – C – Cl
CH3 CH3 CH3

CHEMICAL PROPERTIES:
Halogen atoms being more electronegative than carbon means that the C – X
bond is highly polar due to the presence of partial induced charge where the
halogen is partially negative and carbon is partially positive.

The polarity of the C – X bond makes alkyl halides to be very reactive to the
nucleoptile thus necleophillic substitution.

+ −
−𝐶 𝛿 − 𝑋 𝛿 − 𝐶 − + 𝑋−

:Nu Nu

The type of halogen present also determines the reaction.

The electronegativity difference between the halogen together with the bond
length determines overall the reactivity. Down the group of the halogens there is
decrease in electronegativity and at the same time increase in the bond length.

The reaction becomes faster with Iodo-alkanes than Bromo chloro fluoro alkanes
because of low electronegativity in the iodides.

NUCLEOPHILLIC SUBSTITUTION REACTIONS

(i) Reaction with alkalis:
Alkalis react with alkyl halides to form alcohols when they are refluxed.

CH3Cl + 𝑂̅𝐻(𝑎𝑞) Reflux CH3OH + 𝐶𝑙 − (𝑎𝑞)

CH3 CH CH3 + NaOH(aq) Reflux CH3 CH CH3 + NaI

I OH

96
 CH3 CH3
−
𝑂𝐻(𝑎𝑞)
H3C – C – Br H3 C – C – OH + Br-(aq)
ℎ𝑒𝑎𝑡
CH3 CH3

𝐾𝑂𝐻(𝑎𝑞)
CH2Br CH2OH + KBr.
ℎ𝑒𝑎𝑡

Primary alkyl halides with aqueous alkali.

Primary alkyl halides follow nucleophillic substitution bimolecular (SN2)
mechanism. Is a type of reaction where two molecules involve the rate
determining step.

C - + : X – Alkyl halide
- hydroxide group
Nu

Mechanism:
Transition state fast
𝐶𝐻3𝛿+ − 𝐶𝑙 𝛿−
𝑠𝑙𝑜𝑤 [𝐻𝑂 … . 𝐶𝐻3 … 𝐶𝑙 ] 𝐻𝑂 − 𝐶𝐻3 + ∶ 𝐶𝑙 −

:𝑂̅𝐻

[HO-CH3…Cl]
B
Potential Energy

Transition
State
A ∈𝑎 CH3OH + :Cl-
𝑂̅𝐻 + 𝐶𝐻3 𝐶𝑙 Product C
Reactants

Reaction progress (path)

97
The nucleophille which is 𝑂̅𝐻 approaches the carbon atom carrying
halogen from the opposite side.
This partially forms a nucleophille carbon bond and at the same time, a
carbon halogen bond partly breaks. This leads to the increase in potential
energy from A to B.

At B, there is partial halogen bond broken and partial nucleophille bond

formed. This state is known as activation complex or transition state.

The energy level between the reactants and the activation complex is called
the activation energy.

Later, the potential energy of the system increases when all the carbon
halogen bonds are broken and the carbon nucleophille bonds are formed.

The energy of the system finally decreases until point C where the product
of the alcohol is finally formed. This type of reaction is categorized as SN2
reactions mechanism because there are two molecules involved at the
activated complex.

(ii) Secondary alkyl halide

CH3CHCH3 + NaOH(aq) Heat CH3CHCH3 + NaCl
Cl OH

Mechanism:
H𝑂̅: OH

CH3 – CH 𝛿+ – CH3 CH3 – CH – CH3 + :C𝑙 −

𝐶𝑙 𝛿−
:𝐶𝑙 − + Na+(aq) NaCl.

The mechanism followed by secondary alkyl halides is always between

SN1 and SN2.

(iii) Tertiary alkyl halides

98
 CH3 CH3
H3C – C – Br + 𝑂̅H(aq) reflux H3C – C – OH + 𝐵𝑟 − (aq)

CH3 CH3

Tertiary alkyl halides follow SN1 mechanism. Here only the alkyl
halide molecule is involved in the activated complex and thus its
concentration alone determines the order of reaction.

Mechanism:
CH3 CH3

𝑆𝑒𝑙𝑓
H3C – C – Br C+
𝐼𝑜𝑛𝑖𝑠𝑎𝑖𝑜𝑛
H3C CH3 + :𝐵𝑟 −
CH3

CH3 CH3
H𝑂̅:
C+ Fast HO – C – CH3
CH3 CH3 CH3

REACTIONS WITH ALKA OXIDES (Na, K)

Alkyl halides react with sodium or potassium alka oxides to form ethers
under heat.

̅ Na+
CH3CH2Cl + CH3O heat CH3CH2OCH3 + NaCl.
Ethoxy methane.

CH2Br + CH3CH2ONa CH2OCH2CH3 + NaBr.

Bromo phenyl methane Phenyl methoxy ethane

Mechanism:

99
 ̅ Na+
CH3CH2O slow ̅ (aq) + Na+
CH3CH2O

CH3CH2O: CH2δ+ − 𝐵𝑟 𝛿−
fast CH2OCH2CH3 + Br-.

Na+(aq) + Br-(aq) NaBr.

REACTIONS WITH SILVER SALTS OF CARBOXYLIC ACIDS

Alkyl halides react with silver salts of carboxylic acids when refluxed to form
esters. This reaction uses the alkanoate ion as the nucleophille.
O
̅ Ag+ + CH3CH2 Cl
CH3 COO Reflux CH3 C OCH2 CH3 + AgCl
Ethyl Ethanoate

O O
ℎ𝑒𝑎𝑡
̅ Ag+
C-O + CH2Br C – O – CH2 + Ag Br
𝑟𝑒𝑓𝑙𝑢𝑥

CH3 CH3 O
̅ Ag+
CH3 – C – Cl + HCOO H3C – C – O CH + AgCl
CH3 CH3
2, 2 dimethyl, ethyl methanoate.

Mechanism:
CH3 CH3
CH3 – C – Cl slow C+ + Cl-
CH3 H 3C CH3

O O
̅ Ag+
HCO ̅ + Ag+.
HC-O

100
 O CH3 CH3 O
H – C𝑂̅:
C+ Fast H3C – C – O CH3
H3C CH3 CH3

Ag+(aq) + Cl-(aq) AgCl(s).

REACTIONS WITH POTASSIUM CYANIDE (KCN)

Alkyl halides react with KCN in presence of an alcohol when refluxed to form
alkyl nitriles.

Condition (reflux) – alcohol present.

Nucleophile C̅ ≡ N or C̅N.

Example:
ℎ𝑒𝑎𝑡
CH3CH2CH2Cl + KCN CH3CH2CH2CN + KCl
𝑟𝑒𝑓𝑙𝑢𝑥
Propyl nitrile.

CH2Br + KCN heat CH2CN

Phenyl methyl nitrile.

Mechanism:
KCN K+ + C̅N.

NC̅:

CH2δ+ − Br δ− CH2 − CN+∶ Br −

K+(aq) + Br-(aq) KBr.

Note:

101
(i) The above reaction is important inorganic synthesis, more especially
increasing the carbon length (chain) by a single carbon.

(ii) Silver cyanide can also be used instead of potassium cyanide.

Convert CH3COOH to CH3CH2COOH.

REACTIONS WITH SILVER NITRITE (AgNO2).

Alky halides react with AgNO2 when refluxed to form a mixture of nitro alkanes
and alkyl nitrite. Such types of reactions are not important in synthesis since they
yield a mixture of products.

CH3 NO2 Nitro methane

ℎ𝑒𝑎𝑡
CH3 Cl + AgNO2
𝑟𝑒𝑓𝑙𝑢𝑥
CH3O – N = O Methyl nitrite.

Mechanism:
AgNO2 ̅ 2.
Ag+ + NO

̅:
O = N-O

CH3δ+ − Clδ− CH3 O − N = O + Cl−

Methyl nitrite

Ag+ + Cl- Ag Cl-(aq)

Or:
O = N̈ - O
̅:
CH3δ+ − Clδ− CH3 N𝑂2 = O + Cl−
Nitro methane

Ag+ + Cl- AgCl.

102
 REACTIONS WITH AMMONIA AND AMINES

Alkyl halides react with conc. NH3 to form a mixture of amines when heated in a
sealed tube. A mixture of amines are produced because a product at one stage
become a nucleophille for the next stage. The nucleophille is ammonia and the
amines.

ℎ𝑒𝑎𝑡 𝑖𝑛
CH3 CH2 – I + NH3 CH3 CH2 NH2 + HI
𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
Ethyl amine (Primary)

ℎ𝑒𝑎𝑡
CH3 CH2 – I + CH3 CH2 NH2 CH3 CH2 NH CH2 CH3 + HI
𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
Diethyl amine (Secondary)

CH2 CH3
ℎ𝑒𝑎𝑡𝑒𝑑
CH3 CH2 – I + CH3 CH2 NH CH2 CH3 CH3 CH2 N – CH2 CH3
𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
Triethyl amine (Tertiary)

ℎ𝑒𝑎𝑡
CH3 CH2 – I + (CH3 CH2)3N (CH3 CH2)−
4 N
𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
Tetra ethyl amine
(Quaternary amine)

ELIMINATION REACTIONS OF ALKYL HALIDES

These are reactions that will result into the formation of unsaturated compound
with elimination of a water molecule. Alkyl halides when refluxed or heated
with an alkali (KOH, NaOH) in the presence of an alcohol, they from alkene. The
reaction can also be effected by using a strong base which is an alka oxide.

Strong base (Alka oxide)

̅
Ethanoxide / 𝜖tO
Methoxide /met O ̅

103
 DEHYDROHALOGENTION
𝑁𝑎𝑂𝐻(𝑎𝑞)
CH3 CH2 Cl ̅
CH2 = CH2 + HCl
𝜖𝑡O

𝑂̅𝐻(𝑎𝑞) /𝜖𝑡𝑂𝐻
CH3 CH CH3 CH2 = CH CH3 + HBr.
ℎ𝑒𝑎𝑡
Br

CH3 CH3
𝜖𝑡𝑂̅/𝑚𝑒𝑡𝑂̅𝐻
H3 C – C – Cl CH2 = C – CH3 HCl
ℎ𝑒𝑎𝑡
CH3 2-methyl/prop-1-ene.

Cl
𝜖𝑡𝑂̅𝑁𝑎𝑚𝑒𝑡𝑂𝐻
CH CH3 CH = CH2 + HCl
ℎ𝑒𝑎𝑡

Phenyl ethene

Cl
𝐸𝑥𝑐𝑒𝑠𝑠 𝜖𝑡𝑂̅𝐾 + /𝜖𝑡𝑂𝐻
CH CH2 Cl C≡CH + 2HCl
ℎ𝑒𝑎𝑡

Phenyl ethyne

Mechanisms:
Elimination bimolecular (𝜖2 ).

𝜖t𝑂̅𝑁𝑎+ + 𝑂̅𝐻(𝑎𝑞) ̅ 𝑁𝑎+ + 𝐻2 𝑂

𝜖𝑡O

𝜖𝑡𝑂̅𝑁𝑎+ 𝜖𝑡𝑂̅ : + 𝑁𝑎+ .

H3C – CH CH3 H2C = CH CH3 + Br- + 𝜖tOH

H Br

𝜖t𝑂̅: N𝑎+ + Br- NaBr.

104
𝜖𝑡𝑜̅ 𝐾 + (𝑎𝑞) 𝜖𝑡𝑂̅(𝑎𝑞) + 𝐾 + (𝑎𝑞).

Cl Cl Cl
C CH3 𝜖𝑡𝑂𝐻 C = CH2 + Cl-
H
𝜖𝑡𝑂̅:

Cl
C = CH C ≡ CH2 + Cl-
H
𝜖tO:

Cl-(aq) + K+ KCl

Elimination unimolecular (𝝐1)

CH3 CH3
𝐼𝑜𝑛𝑖𝑠𝑎𝑡𝑖𝑜𝑛
H3C – C – Cl C+ + :Cl-
𝑠ℎ𝑜𝑤

CH3 H3C CH3

CH3 CH3
C+ met OH H3C – C = CH2 + 𝜖tOH
H3 C CH2

𝜖t𝑂̅:

Research: Discus all the reactions of chloro ethane with NaOH. (25mks)

Wurtz reaction:
When alkyl halides are reacted with Na metal in the presence of ether,
alkanes are formed. The product will have an increased carbon atom by 2
i.e. the carbon number doubles.

105
 2 R – X + 2Na dry ether R – R + 2NaX.
Akane.

2CH3Cl + 2Na dry ether CH3 CH3 + 2NaCl.

CH3 CH3 CH3 CH3

CH3 CH Cl Na/dry ether CH3 CH CH CH3 + 2NaCl
CH3 CH3
CH3 CH CH CH3

2𝑁𝑎
CH2Br CH2 – CH2 + 2NaBr.
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

DIHALIDES COMPOUNDS

There are compounds that have got two halogen atoms within the same carbon
chain.

There are two types of dihalides;

(i) Vicinal dihalide
This contains two halogen atoms located on any adjacent carbon atom i.e.
H2C – CH2
X X

Example:
CH2 Cl CH2 Cl 1, 2-dichloro ethane.

Br
CH3 CH CH CH3 2, 3-dibromo butane.
Br

Cl
CH CH2 Cl 1, 2-dichlorophenyl ethane.

106
(ii) Gem dihalides
These contain the two halogen atoms located on the same carbon atoms.
i.e. X
CH3 – C – CH3
X
Example:
Cl
CH3 C – CH3 2, 2 dichloro propane
Cl

CH3 CH Cl2 1, 1-dichloro ethane.

PREPARATION OF DIHALIDES

Dihalides are prepared from the following reactions:

(i) From Alkenes
When alkenes are reacted with halogens in presence of CCl4 (organic base)
at room temperature, a vicinal dihalide is formed.
𝐶𝐶𝑙4
CH2 = CH2 + Cl2 Cl CH2 CH2 Cl.
𝑅.𝑇

(ii) From alkynes and halogen acids

When alkynes react with halogen acids (excess), a gem dihalide is formed.
Br

CH3 C ≡ CH + 2HBr heat CH3 C – CH3

Br

𝑅𝑂𝑂𝑅
HC ≡ CH + 2HCl H3C – C Cl2.
ℎ𝑒𝑎𝑡

(iii) From carbonyl compounds (Aldehydes and Ketones).

When a carbonyl compound is reacted with phosphorous Penta / tri
chloride, a dihalide is formed. Using aldehydes, will produce a gem
dihalide and ketones also produce gem dihalide.

107
 O
CH3 C - H + PCl5 CH3 CH Cl2 + POCl3

O Cl
CH3 C CH3 + PCl5 CH3 – C – CH3 + POCl3
Cl

POLYHALIDES
These are halogen compound with more than two halogen atoms on the same
carbon chain.

AROMATIC HALIDES
These are compounds with one or more halogen atoms directly attached to the
aromatic ring.

X or Ar – X

Cl Cl Br

Cl Br Br
Chloro benzene 1, 3-dichloro benzene 1, 3, 3-tribromo benzene.

PREPARATION

Electrophic substitution
𝐶𝐻3𝑥 / 𝐴𝑙𝑥3 /ℎ𝑒𝑎𝑡
X
𝑋2 /𝐹/ℎ𝑒𝑎𝑡

CH3 CH3 CH3

𝐶𝐻3𝑥 /𝐴𝑙𝑥3
x +
ℎ𝑒𝑎𝑡

108
 From benzene diazonium salt

CuCl/Conc. HCl Cl
Conc.

CuBr/HBr Br

KI I
NH2
𝑁𝑎𝑁𝑂2 +
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙<10𝑜 𝐶 𝑁≡ 𝐶𝑙
+𝑁2 𝐵𝑟4−
HBr4 F
ℎ𝑒𝑎𝑡
Phenyl
Amine

PHYSICAL PROPERTIES OF AROMATICS

They are colourless liquids or solids with characteristic flame.

They are insoluble in H2O but soluble in organic solvents like CC l4.

NOTE:
They do not easily undergo nucleophillic substitution unlike alkyl halide.

Distinguish between Cl and CH2Cl

Reagent: Hot aqueous NaOH in dilute HNO3 and AgNO3.

Observations: - A white precipitate forms with CH2Cl.

- No observable change with Cl.

109
 ALCOHOLS AND PHENOLS:
These are compounds that contain hydroxyl group. Therefore, the functional
group is hydroxyl group. The difference between alcohol or alkanols and phenol
is that the hydroxyl group is directly attached to the aromatic ring in phenols.

Alkanol Phenol
R – OH Ar – OH

OH

ALKANOLS OR ALCOHOLS

Alcohols are organic compounds derived from hydro carbons but where one or
more hydrogens is/are replaced by hydroxyl group. The general formula is
R – OH where R is an alkyl group or simply represented as CnH2n+1 OH. Where
n = simple number.
They are also called alkanols simply because a hydroxyl group replaces a
hydrogen.

TYPES OF ALCOHOLS

There are basically three types of alcohols:

(i) Monohydric alcohol
This is one that has got one hydroxyl group.

(ii) Dihydric alcohol

This is one that has got two hydroxyl groups.

(iii) Polyhydric alcohol

These have got more than two hydroxyl groups e.g.
HO – CH2 CH CH2 OH
OH

NOMENCLATURE

110
Alcohols are named as alkanols according to the IUPAC. This is done by
replacing the last “e” in alkane name with suffix “ol” (functional group name).

The position of the functional group has to be indicated just before the suffix “ol.

If the stem name has got a vowel, then a consonant letter must be added just
before the position of the functional group.

E.g. CH3 CH2 OH Ethano-1-ol

CH3CH CH3 Propan-2-ol

OH

CH3
CH3 C CH2 CH3 2-methyl butan-2-ol.
OH

HO – CH2CH2OH Ethane-1, 2 – diol

HO – CH2CH (OH) CH2 OH Propane – 1, 2, 3 – triol.

OH Cyclohexan-1-ol

CH3
CH3 C – OH 2-methyl propan-2-ol
CH3

OH
Cyclohexan-1, 3-diol
Xyclohexane-1, 3-diol
OH

CH2OH

111
 Phenyl methan-1-ol.

NOTE: Look at isomerism in alcohols.

Types – structural:
(i) Chain
(ii) Position
- Functional (alcohol and others are isomeric).

CLASSES OF ALCOHOLS
Monohydric alcohols are classified into three classes.
(i) Primary alcohol
This has one alkyl group attached to the carbon atom carrying the –OH
group. E.g. - C – OH
H

CH3CH2 – OH

(ii) Secondary alcohol

This has got two alkyl groups attached to the carbon atom carrying the OH
group.

H - C – OH

E.g: CH3 CH CH3

OH

(iii) Tertiary alcohol

This has three alkyl groups attached to the carbon atom carrying the OH
group.
- C – OH

E.g. CH3
CH3 - C – OH
CH3

METHODS OF PREPARATION
112
(i) From alkyl halide (SN reaction)
When alkyl halides are refluxed with aqueous alkali (KOH or NaOH) or
with moist silver oxide, alcohols are formed.

This is a hydrolysis reaction that occurs by nucleophillic substitution

reaction.

CH3 CH2 Cl + NaOH(aq) warm CH3 CH2 OH + NaCl

I OH
CH3 – C – CH3 + 𝑂̅H(aq) heat CH3 – C – CH3 + I-
CH3 CH3

Br + KOH(aq) heat OH + KBr.

Cl OH
CH3 CH CH3 + AgOH(aq) CH3 CH CH3 + AgCl.

(ii) From alkenes

When alkenes are reacted with dilute mineral acid water and heated, an
alcohol is formed. They usually used acid is H2SO4 acid.

If the mixture is not heated, then an alkyl hydrogen sulphate is formed.

OH
𝐻 + /𝐻2 𝑂
CH2 = CH CH3 H – CH2 CH2 – CH3
ℎ𝑒𝑎𝑡

CH2 = CH CH3 H2SO4/H2O CH3CH2 CH3

HSO4

Mechanism:
𝐻𝛿+ − 𝑂𝛿− 𝑆𝑂3 𝐻

CH3 CH = CH2 H+ CH3 - +CH CH3.

113
 CH3 +CH CH3 CH3 – CH – CH3 -H+ CH3 CH CH3 + H+

ÖH2 O+ OH
H H

OR:
CH3 CH = CH2 𝐻𝛿+ − 𝑂𝛿− 𝑆𝑂3 𝐻 ̅ SO3H
CH3 +CH CH3 + O

CH3+CH CH3 CH3 CH CH3

OSO3H
̅ SO3H
:O H2O/heat

NOTE:
H2O acts as a nucleophile that will react with the alkyl hydrogen sulphate
in the last step to form an alcohol. i.e.
:OH2 H H
O+
CH3 CH CH3 CH3 – CH CH3 -H+ OH

OSO3H CH3 CH CH3

When alkenes are reacted with H2O in presence of Al2O3, an alcohol is

formed. E.g.
𝐴𝑙2 𝑂3
CH3CH = CH2 + H2O OH
ℎ𝑒𝑎𝑡
CH3 CH CH3

𝐴𝑙2 𝑂3
+ H 2O OH
ℎ𝑒𝑎𝑡

CH3 CH3
𝐴𝑙2 𝑂3
CH3 C = CH2 + H2O CH3 C – CH3
ℎ𝑒𝑎𝑡

OH

(iii) From carbonyl compounds (Aldehydes and ketones)

114
 Carbonyl compounds are reduced in the presence of a suitable reducing
agent to alcohols.

Aldehydes [H] Primary alcohols

Ketones [H] Secondary alcohols

Reducing agents normally used:

Hydrogen in presence of catalyst, Ni/150, Pt/pd, r.t.p.
Using LiAlH4 (Lithium, Aluminum, Tetra hydride) in presence of dry
ether.
Sodium boron tetrahydride (NaBH4)

E.g.
O
𝑁𝑖
CH3 CH2 CH + H2 H3CH2CH2OH
150𝑜 𝐶
Propanal Propanol

O
CH3 C CH3 + H2 Ni /150oC CH3 CH CH3
OH

O
𝐿𝑖𝐴𝑙𝐻4
CH3 CH CH3 CH2 OH
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

CH3 C CH2 CH3 NaBH4 CH3 CH CH2 CH3

O OH

𝐿𝑖 𝐴𝑙𝐻4
CH3CH = CH2CH2 OH
𝐷𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
O
CH3 CH = CH C H
𝐻2 /𝑁𝑖
CH3 CH2 CH2CH2 OH
150𝑜 𝐶

(iv) Hydrolysis of esters

115
 Esters are hydrolyzed in presence of mineral acids or alkalis to form
corresponding alcohols and carboxylic acids. This reaction is not very
useful for synthesizing alcohols because of the mixture of alcohol and acid.

O
𝐻 + (𝑎𝑞)
CH3 C OO CH2 CH3 CH3 COOH + CH3 CH2 OH
ℎ𝑒𝑎𝑡

O
𝑂𝐻(𝑎𝑞)
CH3 O C CH3 CH3 OH + CH3 COOH
ℎ𝑒𝑎𝑡
Ethyl ethanoate

Mechanism: (look for acid/base hydrolysis of esters).

(v) From primary amines

They react with HNO2 acid which is generated “insitu” by reacting sodium
nitrite and conc. HCl to form alcohols. This reaction is only for primary
amines and not secondary or tertiary.
𝑁𝑎 𝑁𝑜2 /𝐻𝐶𝑙
CH3 NH CH3OH + N2 + H2O
ℎ𝑒𝑎𝑡

𝑁𝑎 𝑁𝑜2 /𝐻𝐶𝑙
CH2 NH2 CH2 OH + N2 + H2O.
ℎ𝑒𝑎𝑡

(vi) From fermentation of carbohydrates.

116
 PROPERTIES OF ALCOHOLS

PHYSICAL PROPERTIES
Lower members are liquids, higher members are solids at r.t.p with x-tic smell.
The lower members are very soluble in H2O but the solubility decreases with the
molecular mass.
Alcohols have got relatively higher boiling points compared to similar hydro
carbons of approximately the same molecular mass.

Examples:
Molecular weight Boiling points
Ethane 30 -42
Methanol 32 46
Butane 58 -0.5
Propan-ol 60 98

Graph showing the variation of boiling points (oC) of different compounds with
molecular weight. A

300 B

C
200
D

100
Boiling point

0
(oC)

A – Carboxylic acids
B - Alcohols
-100 C - Amines
D – Alkanes

-200

Molecular weight
Note:
The boiling points increase generally with increase in molecular weight.

117
Increase in molecular weight increases the VanDer Waal’s forces of attraction.
This makes the compound stronger hence high boiling points.

Explanation:
The boiling points of the compounds above on the graph are determined by
hydrogen boding.
Carboxylic acids have got the highest boiling points due to extensive hydrogen
bonds which makes molecules to dimerise in a liquid hence difficult to separate
them during boiling so that they escape to vapour.

O HO CH3
C
C
H3 C OH O

Hydrogen bonding.

Alcohols’ boiling point is higher than that of alkanes but lower than that of
carboxylic acid because of inter and intramolecular hydrogen bonding.
Molecules will interact in liquids and aqueous phases and high boiling point.

CH3 Inter-hydrogen bond

H C C H O H

H H
H
Intra-hydrogen
Bond H–O–C–H

CH3

Amines boil at a lower temperature than alcohols of the corresponding molecular

weight because nitrogen is less electronegative than oxygen so the hydrogen
bonds formed in amines are weaker than in alcohols thus amines boil at a lower
temperature.
Alkanes have the least boiling point because of the absence of hydrogen with
only Van der Waal’s forces of attraction which are weaker and easily broken
during boiling.

118
In summary:
The solubility in water and the boiling points of alcohols are due to hydrogen
bonding.

Questions:
1. Methyl amine (mm = 31) boils at -6.3oC while methanol (mm = 32) boils at
46oC. Explain.

2. 2-methyl propan-2-ol boils at a lower temperature than butan-1-ol yet they

all have the same molecular weight.

OH
CH3 C CH3 and CH3 CH2CH2CH2 OH
CH3

2 methyl propan-2-ol is highly branched giving it a spherical shape which

decreases on the size and weakens the Van der Waal’s forces of attraction
existing between the molecules.

Butan-1-ol is a straight chain molecule which gives it an extended structure

resulting in relatively stronger Van der Waal’s forces.

119
 CHEMICAL PROPERTIES OF ALCOHOLS

Alcohols consists of three major bonds that are involved in a chemical reaction.
(i) Functional group – OH group.
Where the O – H bond is involved in the reaction.
(ii) Oxygen-carbon bond which is highly polarized.
(iii) Alkyl groups – R group.

REACTION INVOLVING CLEAVAGE OF THE O – H BOND

Reactions with electropositive metals:

When an alcohol is reacted with a metal like sodium or potassium, an alka oxide
and H2 gas are formed.

2R – OH + 2Na(s) ̅ Na+ + H2
2R – O

CH3 CH2 OH + Na(s) r.t.p ̅ Na+ + H2(g)

2CH3CH2O

CH2 – OH + 2K(s) ̅ Ka+ + H2(g)

CH2O

Observation:
Effervescence of a colourless gas that burns with a pop sound.

Reactions with mineral acids:

When an alcohol is reacted with a mineral acid, a salt is formed.

R – OH + HCl R-+
OH2 Cl

CH3 CH2 OH + HCl CH3 CH2 +

OH2 Cl

From the two reactions above, alcohols are regarded as amphoteric because they
react with acids and bases to show both acidic and basic.

Esterification
Alcohols react with carboxylic acids in presence of mineral acids to form esters.
This reaction is known as esterification.

120
 O
𝐻+
CH3 CH2 OH + CH3 CH2 COOH CH3CH2 COCH2CH3 + H2O
ℎ𝑒𝑎𝑡
Ethyl propanoate

𝐻+
COOH + CH3 CH2 OH O
ℎ𝑒𝑎𝑡
COCH2 CH3 + H2O

Ethyl benzoate.

Mechanism:
O: O+ H
C–O–H C–O- H
H+

O+ H O-H
C – OH C–O–H
CH3CH2 – O – H
CH3CH2ÖH
-H +

O H O:
C 𝑂+ – CH2 CH3 C – OH

CH3CH2 – O – H
-H +
O
C – O CH2 CH3

121
Alcohols react with acid chlorides to form esters.
O O
CH3CH2OH + CH3 C Cl CH C OCH2 CH3 + HCl
Ethanol
Chloride

O
CH3OH + HCOCl HC OCH3 + HCl

O O
OH + CH3 C Cl COCH3

Cyclo hexayl ethanoate.

Mechanism:
O :O- H O H
C - 𝐶𝑙 𝛿− H – C – 𝑂+ - CH3 HC – 𝑂+ – CH3
H 𝛿+
Cl
CH3ÖH -H+

O
H C – O – CH3

Alcohols react with acid anhydrides to form esters.

O O O O
R1 – C – O – C – R2 + R3 – OH 𝐻+ R1 – C – OR3 + R2 – C – OH

O O O
CH3 C – OCH3 + CH3 OH H+ CH3 C – OCH3 + CH3 COOH
Ethanoic acid Methyl ethanoate
anhydride

122
Alkylation of alcohols
Alcohols react with dialkyl sulphates to form ethers and alky derivatives. This
reaction involves replacement of hydrogen in the alcohol with alkyl group.

R – OH + R2SO4 R – O – R + RHSO4

CH3CH2OH + (CH3)2SO4 CH3CH2OCH3 + CH3 HSO4

Dimethyl Ethoxy methane Methyl hydrogen
Sulphate sulphate

CH2OH + (CH3CH2)2SO4 CH2OCH2CH3 + CH3CH2HSO4

REACTIONS INVOLVING CLEAVAGE OF A CARBON OXYGEN BOND

In these reactions, we are removing both oxygen and hydrogen atoms from the
alcohol.

Reactions with halogen acids (Hx)

Alcohols react with halogen acids to form alkyl halides.

CH3OH + HCl CH3Cl + H2O.

CH3CH2OH + HI CH3CH2I + H2O.

CH2OH + HBr CH2Br + H2O.

CH3 – CH – OH + HCl CH3 CH – Cl + H2O

CH3 CH3

CH3 CH3
CH3 – C – OH + HCl CH3 – C – Cl + H2O
CH3 CH3

123
Mechanism:
Primary and secondary alcohols follow SN2 mechanism because of the fairly
unstable carbon cation ion, while the tertiary alcohols follow SN1 because of the
stability of the carbon cation ion formed.

SN2:

CH3 CH2 ÖH + 𝐻𝛿+ − 𝐶𝑙 𝛿− slow CH3CH2O+ H2 + Cl-

CH3CH2 - +𝑂𝐻2 fast CH3CH2 – Cl + H2O

:Cl-

SN1:
CH3 CH3
CH3 – C – OH C+ + ̅ H(aq)
O
CH3 H3C CH3

H – Cl H+ + Cl-

CH3 CH3
:Cl-
C+ CH3 – C – Cl

CH3 CH3 CH3

̅H
H+ + O H2O.

124
 PRACTICAL IMPORTANCE OF THE REACTION
The practical importance of the above reaction is to distinguish between the three
classes of alcohol.

Reagent: An hydrous zinc chloride in concentrated hydrochloric acid.

Observation:
- An immediate cloudy solution at room temperature forms with a tertiary
alcohol.
- Within 5 minutes at room temperature, a cloudy solution is formed with a
secondary alcohol.
- No cloudy solution forms at room temperature with primary alcohol.

Equations:
Anhydrous Cl
CH3 CH CH3 + HCl ZnCl2 CH3 CH CH3 + H2O
Conc.
OH

CH3 CH3

H3C – C – OH + HCl(l) ZnCl2(s) H3C – C – Cl + H2O

Conc.
CH3 CH3

REACTIONS WITH PHOSPHORUS HALIDES

Alcohols react with PX5 and PX3 to form alky halides where X is a halogen.

3CH3 CH2 OH + PCl3 3CH3CH2Cl + H3PO3

CH3CH2OH + PCl5 CH3CH2Cl + HCl + POCl3

Others: PI3/PI5
PBr3/PBr5.

NOTE:
Evolution of HCl or fuming whenPCl5 is added to a compound suggests the
presence of OH group in that compound.

125
 REACTION WITH THIONLY CHLORIDE
Alcohols react with SOCl2 or SOBr2 to form alkyl halides. An organic base like
pyridine must be included to neutralize toxic and poisonous gases liberated.

CH3CH2 OH + SOCl2 pryridine CH3CH2Cl + SO2 + HCl.

CH2OH + SOBr2 CH2Br + SO2 + HBr.

Mechanism:

REACTION WITH H2SO4 ACID

Alcohols react with H2SO4 giving different products depending on the conditions
of reaction.

Conditions:
A. (i) Conc. H2SO4 Products got are substituted products.
(ii) Excess alcohol
(iii) Low temperatures.
Substituted products.
Alky hydrogen sulphate – 0oC.
Ether – warm (140oC)

B. (i) Conc. H2SO4.

(ii) High temperatures (heat) - Elimination product.
(iii) Limited alcohol.

Example:
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2OH CH3CH2HSO4 + H2O.
0𝑜 𝐶

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH2OH CH2HSO4 + H2O.
0𝑜 𝐶

Phenyl methyl
Hydrogen sulphate.

126
Mechanism:

CH3 CH2 ÖH

𝐻𝛿+ − 𝛿−
𝑂𝑆𝑂3 𝐻 CH3CH2𝑂+ 𝐻2 + 𝑂̅𝑆𝑂3 𝐻

CH3 CH2 - +𝑂𝐻2 −𝐻2 𝑂 CH3 +CH2 + H2O.

CH3 +CH2 CH3CH2HSO4

:OSO3H.

Excess
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
2CH3CH2OH CH3CH2O CH2 CH3 + H2O
140𝑜 𝐶
Diethyl ethers

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
2CH3OH CH3 O CH3 + H2O.
140𝑜 𝐶

Mechanism:

CH3 CH2 ÖH

𝐻𝛿+ − 𝛿−
𝑂𝑆𝑂3 𝐻 CH3CH2 +𝑂𝐻2 −𝐻2 𝑂 CH3 +CH2

[CH3 CH2 OH] >> [𝑂̅𝑆𝑂3 ] therefore CH3CH2OH is a better nucleophile.

CH3 CH2ÖH +CH3CH2 CH3CH2 – O – CH2 CH3

-H+

CH3CH2 O CH2 CH3

Alcohols are dehydrated when heated with conc. H2SO4 and H3PO4 acid to form
alkenes in a liquid phase or when the alcohol is passed over heated Al2O3 at 300o
in a vapour phase.

Water molecule is eliminated and therefore this type of reaction is known as

elimination or dehydration.

127
The reactivity in the liquid phase is determined by the type of carbon cation ion
formed.

Elimination reactions occur under the following conditions:

(i) Heat: [170 – 185oC] Primary alcohol
[150 – 180 C]
o Secondary alcohol
[90 – 150 C]
o Tertiary alcohol.

(ii) Conc. H2SO4: [>60%].

Example:
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2CH2OH CH3 CH = CH2 + H2O
175− 185𝑜 𝐶

𝐶𝑜𝑛𝑐.𝐻3 𝑃𝑂4
CH3 CH CH3 CH3CH = CH2 + H2O
ℎ𝑒𝑎𝑡
OH

CH3 CH3
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
H3C – C – OH H3C C = CH2 + H2O
150𝑜 𝐶
CH3

CH2 CH2 OH Conc. H3PO4 CH2 = CH2 + H2O.

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2CH2CH2OH CH3CH = CH CH3 + H2O.
175𝑜 − 185𝑜 𝐶

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3 CH2CH2CH3 CH3CH = CH CH3 + H2O.
175
OH

Mechanism:
1. Protonation of alcohol
2. Loss of H2O to form carbo cation ion.
3. Re-arrangement of the carbo cation to a more stable form.
4. Loss of the proton to form alkene.

128
 CH3 CH3
H3C – C - ÖH + H δ+ − Oδ− SO3 H ̅ SO3 H
H3 C − C − O+ H2 + O
CH3 CH3

CH3 CH3
H3C – C – OH3 -H2O C + H 2O

CH3 H3C CH3

CH3 CH3
H3C – C
CH2 CH3 C = CH2 + H2SO4.
H

𝐻𝑂3 𝑆Ö

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2CH2CHOH CH3CH = CH CH3 + H2O
175−185𝑜 𝐶

CH3CH2CH2CH2ÖH H+ CH3CH2CH2CH2 +𝑂𝐻2

CH3CH2CH2C𝐻2− +𝑂𝐻2 -H2O CH3CH2CH2+CH2 + H2O

[Unstable(Io1)]

CH3CH2CH +CH2 CH3CH2+CHCH3

[Stable (IIo)]
H

CH3CH +CH CH3 CH3CH = CHCH3 + H2SO4.

̅:
HO3SO

129
 DEHYDRATION IN VAPOUR PHASE

When an alcohol is heated and its vapour is passed over heated Al2O3 at 300o, an
alkene is formed which is detected by turning bromine water colourless.

Silca
Aluminium oxide

Heat(300oC)

Heat Bromine water

Cotton wool Brown - colourless
Soaked in alcohol

𝐴𝑙2 𝑂3
CH3CH2OH CH2 = CH2 + H2O.
𝐻𝑒𝑎𝑡(300𝑜 𝐶)

𝐴𝑙2 𝑂3
CH2CH2OH CH = CH2 + H2O.
𝐻𝑒𝑎𝑡

N.B: Elimination reactions in alcohols compete with substitution reactions. The

difference is due to the conditions provided.
Heat
Conc.H2SO4(180o)
CH2=CH2 + H2O

CH3CH2OH

𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4
CH3CH2OCH2CH3 + H2O
𝐸𝑥𝑐𝑒𝑠𝑠 𝑎𝑙𝑐𝑜ℎ𝑜 (140𝑜 )

130
 OXIDATION REACTIONS

Primary alcohol [O] Aldehyde [O] Carboxylic acid.

Secondary alcohol [O] Ketones [O] No product

Tertiary alcohols [O] No product.

Oxidation of alcohols is effected by oxidizing agents such as:

(i) Acidified K2Cr2O7/ H+(aq)
(ii) Acidified Na2Cr2O7/H+(aq)/Cr2𝑂72− (𝑎𝑞)
(iii) Chromic acid, CrO3.

Acidification is done by use of sulphuric acid.

CH3CH2OH + Na2Cr2O7 + H2SO4 heat CH3CHO + Na2SO4 + Cr2(SO4)3 + H2O

3CH3CH2OH + Na2Cr2O7 + 4H2SO4 heat 3CH3CHO + Na2SO4+ Cr2(SO4)3 + 7H2O

Orange solution Green solution
(Cr2𝑂7 )
2−
(Cr3+)

During the process, the solution mixture turns from orange to green indicating
the conversion of the dichromate to chromium(III) ion.

Excess oxidizing agent.

CH3CHO + Na2Cr2O7(aq) + H2SO4(aq) CH3COOH+Na2SO4(aq) +Cr2(SO4)3 + H2O(l)

Simply:
𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72− (𝑎𝑞)
CH3CHCH3 CH3 C CH3
ℎ𝑒𝑎𝑡
OH

𝐸𝑥𝑐𝑒𝑠𝑠 𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72− (𝑎𝑞)

CH3OH HCOOH
ℎ𝑒𝑎𝑡

131
 𝐻 + /𝐶𝑟2 𝑂72−
CHO COOH
ℎ𝑒𝑎𝑡

IODO FORM/HALO FORM TEST

This test is usually performed to confirm for the presence of compounds that
have got a methyl group.

Example:
OH
Methyl alcohol H3C – CH

H
Methyl at dehydes H3C – C
O

Methyl ketones H3C – C –

O
Product formed CHI3 - Tri iodo methane (Yellow ppt)

This test confirms / differentiates methyl / alcohols from the rest. Methy
alcohols form tri iodo methane when oxidized which is observed as a yellow ppt,
while the rest of the alcohols no observable change.

Reagent: Hot NaOH Solution in Iodine solution.

Question: Give a reagent that can be used to distinguish between pairs of the
compounds below and state what is observed in each case. Write the
equation for the reaction(s) that take place.

(a) CH3CH2OH and CH3CH2CH2OH

(b) OH OH
CH CH3 and CHCH2CH3

(c) O O
C – CH3 and CCH2CH3

132
Solutions:
(a) Hot sodium hydroxide solution.
With CH3CH2OH - A yellow precipitate is observed.
With CH3CH2CH2OH - No observable change.

(b) Reagent: Hot sodium hydroxide in iodine solution.

With OH - A yellow precipitate is observed.
CHCH3

With OH - No observable change.

CHCH2CH3

(c) Reagent: Hot sodium hydroxide in iodine solution.

With OH - A yellow precipitate is observed.
CHCH3

With OH - No observable change.

CHCH2CH3

Equations:
̅ Na+ + 5H2O.
CH3CH2OH + 4I2(aq) + 6NaOH(aq) heat CHI3 + 5NaI(aq) + HCOO

OH

CHCH3 + 4I2(aq) + 6NaOH(aq) heat CHI3(s) + 5NaI(aq)+ CO𝑂̅Na+ + 5H2O.

OH

CHCH3 + 3I2(aq) + 4NaOH(aq) heat CHI3(s) + CO𝑂̅Na+ + 3H2O(l) + 3NaI.

Rule: Alcohols; 4I2; 6NaOH

Aldehydes/ketones, 3I2; 4NaOH.

133
Example:
O
CH3C CH2CH3 + 3I2(aq) + 4NaOH(aq) ̅ Na+ + 3NaI + 3H2O.
CHI3(s) + CH3CH2COO

AROMATIC ALCOHOLS
These are aromatic compounds with hydroxyl groups. They are divided into
two: Aromatic alcohols and phenols.

(i) Aromatic Alcohols:

These contain an aromatic ring and then the hydroxyl group which is not
directly attached to a ring but attached via the chain on the ring.

CH2OH CH2CH2OH

2-phenyl methanol 2-phenyl ethanol.

CH3
C – OH
CH3
2-phenyl propan-2-ol

(ii) Phenols:
These contain an aromatic ring with one or more OH group directly
attached to the ring.

OH OH OH

OH
Phenol Diphenol
CH3
3-methyl phenol.

OH

HO OH

134
 PHENOLS

Is a class of compounds named as phenols and one or more OH groups are

directly attached to the ring

METHODS OF PREPARATION
1. Benzene sulphonic acid
SO3H
Fuming H2SO4 NaOH S𝑂3− Na+ + H2O.

S𝑂3− Na+ + HCl(aq) ̅ Na+

O

̅ Na+
O HCl(aq) OH + NaCl.

2. Cumene process
CH3
+ CH3CH = CH2 H+ C–H
CH3
2-pheny propane.

CH3 CH3
C–H O2 C–O–O–H O
CH3 CH3 dilH+/H2O OH + CH3 C CH3

3. Aromatic halides
In cumene process, Benzene is reacted with propene in presence of an acid
or halogen carrier like AlCl3 to form two phenyl propane.

Molecular O2 is blown into this product and the intermediate is acid

hydrolysed to give a phenol.

When an aromatic halide is treated with alkali at extremely harsh

conditions like 300oC, 200 atm of pressure and copper, a phenol is formed.

135
 This subsequently strengthens the C – O bond by developing a partial
double bond between C and C and at the same time weakening the O – H
bond by decreasing the electron density and releases a proton easily. This
does not occur in aliphatic aromatic alcohols as ordinary alcohols.

Subsequently, phenols being slightly acidic, under the following:

(i) Very soluble in NaOH or KOH
OH + NaOH 𝑂̅Na+ + H2O

(ii) Phenols react with very reactive metals like Na to form salt and H2.
OH 𝑂̅Na+

2 + 2Na(s) 2 + H2(g)

Acid properties of phenols can be improved by;

Adding electrons with a…………which de-active the ring. Such groups include
the Nitro groups. 2, 4, 6-trinitrophenol is more acidic than phenol. It liberates
CO2 from saturated NaHCO3.

OH ̅ Na+
O
O 2N NO2 O2N NO2
NaHCO3 + + CO2 + H2O

NO2 NO2

Carboxylic acids are more acidic than phenols. [Give the reactions that
distinguish acidic character of phenols and carboxylic acids.

COMPLEX FORMATION WITH NEUTRAL FECL3.

Phenols form a complex with aqueous neutral FeCl3 and the colour of the
complex product is violet colouration (purple). This reaction is important in
confirming the presence of a phenolic group and it is also useful in
distinguishing between phenol and aromatic alcohols.

Question: Distinguish between HCOOH and CH3COOH.

(We use the Iodo form test).

136
 OR:
Using neutral (iron III) chloride) solution.
A purple colouration with HCOOH.
No observable change with CH3COOH.

REACTION WITH ZICN DUST:

Phenol when heated with Zinc dust forms benzene.

OH
+ Zn heat + ZnO.

ALCOHOL REACTIONS OF PHENOLS RESEMBLING

This involves cleavage of C - O bond.

Phenols undergo some reactions resembling alcohol where the C – O bond is

involved.

Esterification:
Phenols react with carboxylic acids, halides and acid an hydride to form an ester.

Carboxylic acids:

OH O
+ H3CCOOH H+ O C CH3 + H2O.

Acid halides:
OH O O
+ C – Cl H+ O–C

Acid an hydride:
O O OH O
CH3 C – OC – CH3 + H+ OC CH3 + CH3 COOH

Ether formation:

137
Phenols react with alka oxides to form ethers.

̅ Na+
OH + CH3CH2 O OCH2CH3 + NaOH

Phosphorous penta halides:

Phenols react with PCl5 liberating HCl gas which fumes in air.

OH + PCl5 Cl + POCl3 + HCl

Reactions with liquid NH3.

REACTIONS OF THE RING IN PHENOL

Due to the presence of the OH group in phenol, phenol undergoes a number of
reactions where delocalized electrons on the ring are involved.

Nitration:
Phenol reacts with conc. H2SO4 and conc. HNO3 acids to form 2-nitro phenol and
4-nitrophenol.

OH OH OH
Conc. HNO3/conc. H2SO4 NO2 +

NO2

Alkylation:
Phenol reacts with alkyl halides in presence of a halogen carrier to form
alkylated product phenol.

OH OH OH
+ CH3Cl Al Cl3 CH3 + + HCl

CH3

A cylation O

138
 C

OH O OH
CH3 C – Cl CO CH3 + AlCl3
Al Cl3 COCH3

Bromine H2O.
When reacted with bromine, H2O phenol forms a substituted poly product of 2,
4, 6 tri bromo phenol which is a white precipitate.

The presence of OH makes phenol to be very reactive. This reaction is very

important in confirming the presence of phenol together with the neutral iron
(III) chloride test.

OH OH
Br Br
+ 3Br2(aq) + 3HBr

Br
White ppt.

OH Br
Convert to

Br Br

OH OH
𝑍𝑛(𝑠)
Br Br
𝐻𝑒𝑎𝑡 𝐵𝑟
+ Br2(aq)
Br
Br Br

139
Hydrogen in presence of heated Ni catalyst.
Phenol can be hydrogenated into cyclo hexanol when reacted with H2 in the
presence of a heated catalyst.

OH OH
3H2 /Ni
heat(200o )

POLYHYDRIC ALCOHOLS

These are alcohols with more than one OH group attached to the same carbon
chain as:

HOCH2CH2OH
CH2OH HOCH2 – CH – CH2

HOCH2 OH

The chemical and physical properties of these types of alcohols are slightly the
same; however, there are slight differences.

Ethane-1, 2-diol boils at a higher temperature.

Ethane-1, 2-diol has two OH group which results into formation of extensive
hydrogen bonds which is difficult to break hence high boiling point.

PREPARATION OF DIOLS

They can be prepared from alkyl halides.

CH3CH2Cl HO CH2CH2OH
̅ /𝜖𝑡𝑂𝐻
Heat 𝜖𝑡O ethane-1, 2-diol

CH2 = CH2 MN𝑂4− /𝑂̅𝐻

heat

140
Alkenes
CH2 = CH2 HOCH2CH2OH

O
C – O – OH
Benzene peroxo acid 200oC/pressure

CH2 – CH2 + H2O2

CH3CH2OH HOCH2CH2OH

180oC Conc.H2SO4 heat

MnO̅ 4 /O
̅𝐻

CH2 = CH2

Reactions of diols are the same as those of monohydric alcohols.

The difference is that excess of the reagent is used.

CH3 CH2 CH2 OH

heat Conc.H2SO4
175oC

OH
heat
CH3CH = CH2 ̅ 4 /O
̅H
CH3CH CH2OH
MnO

141
 CARBONYL COMPOUNDS
These are compounds containing a carbonyl functional group. They are alkanal
(Aldehydes) and Alkanones (Ketones).

These two belong to a group of organic compounds known as carbonyl

compounds with a general formula CnH2nO.

R H - Aldehyde

1R IIR - Ketone

The major difference between aldehydes and ketones is in the presence or

absence of H2 attached onto the carbonyl carbon.

In aldehydes, “H” is to the carbonyl carbon while in a ketone, similar or different

alkly groups are attached to the carbonyl carbon as shown above.

NOMENCLATURE
IUPAC system is used in the naming of both aldehydes and ketones. Generally,
aldehydes are named as alkanals by replacing “e” in the alkane name with –“als”
while ketones are named as alkanones by replacing –“e” with –“ones”.

Alkanals Alkanones
(Formaldehyde) O O
HC – H Methanal CH3 C CH3 Propan-2-ones

(Acetaldehyde) O O
CH3 C – H ethanal CH3 C CH2 CH3 butan-2-ones

142
 O O
CH3 CH2 C - H Propanal CH3 C CH CH3
CH3 3-methyl butan-2-ones

O O
CH3CH2CH2 C – H – Butanal CH3 CH – C – CH2CH2CH3
CH3
2-methyl hexan-3-one

O
CH3CH CH 2-methyl propanal
CH3 O

O Cyclohexa-1, 3-dione.

ISOMERISM
Both aldehydes and ketones exhibit structural and functional isomerism.
In structural isomerism, they show position and chain isomers.
In functional isomerism, both aldehydes and ketones are isomeric within
themselves and with other classes of organic compounds like alcohols and cyclic
ethers.

C4H8O

O
CH3CH2CH2CH Butanal

O
CH3CH C CH3 Butan-2-one

143
 H H
H OH

Cyclic butanol (cyclic alcohol)

H H

H H

H H
H H
O Cyclic ether (Tetacfuran)
H H
H H

C4H8O

CH3CH2CH2CHO Butanal

CH3CH – CHO 2-methyl propanal (Aldehyde)

CH3

CH3 C CH2 CH3 Butan-2-one (Ketone)

O

CH2 – CH2
O Tetrahydrofuran (furan)
CH2 – CH2

CH2 = CH CH2 – CH2 OH But-en-4-ol

(Usaturated alcohol)

Write all the isomers of the compounds with the molecular formula C3H6O.
CH3CH2CHO Propanal (Aldehyde)

O
CH3 C CH3 Propanone (Ketone)

144
CH2 = CH CH2OH Prop-1-en-3-ol.

O
CH2 CH2 Trihyrofuran
CH2

PREPARATION OF CARBONYL COMPOUNDS

They can be prepared from the following:
i) Mild oxidation of alkanol (alcohols)
ii) Carboxylic acids or their salts.
iii) Ozonolysis of alkenes followed by hydrolysis.
iv) Acid hydrolysis of alkynes.
v) Hydrogenation of acid chlorides.
vi) Acylation (aromatic ketones)

OXIDATION OF ALCOHOLS
Primary and secondary alcohols are oxidized in liquid phase using K2Cr2O7 /H+
or Na2Cr2O7/H+, CrO3/H+ to form aldehydes and ketones respectively.

During oxidation process, a colourless solution turns to green solution.

Examples:

𝐻 + /𝐶𝑟2 𝑂72− (𝑎𝑞) 𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72−

CH3CH2OH CH3CHO CH3COOH
𝑤𝑎𝑟𝑚 ℎ𝑒𝑎𝑡
Alcohol Ethanal Carboxylic acid
Aldehyde

OH O
𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72−
CH CH CH3 CH3 C CH3
ℎ𝑒𝑎𝑡

𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72− 𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72−

CH2OH CHO COOH
ℎ𝑒𝑎𝑡 ℎ𝑒𝑎𝑡

145
During the oxidation process, especially for primary alcohols, there will be
further oxidation to carboxylic acid which renders this method ineffective but
this further oxidation can be avoided by carrying out a reaction under low heat
(temperatures) or limiting the amount of the oxidant used.

Oxidation can also be effected under vapour phase. When an alcohol vapour is
passed over heated Cu at 300oC, it is oxidized to an aldehyde or ketone.

Cu
CH3CH2OH(g) CH3CHO + H2
300o C

Cu
CH3 CH CH3 CH3 C CH3 + H2
300o C
OH O

Oxidation under vapour phase can also be brought about when an alcohol
together with limited O2 is passed over heated Ag at 500oC.

𝐴𝑔(𝑆)
CH3 CH2OH + ½ O2 CH3CHO + H2O
500𝑜 𝐶

𝐴𝑔(𝑆)
CH3 C(OH) CH3 + ½ O2 CH3 COCH3 + H2O
500𝑜 𝐶

CARBOXYLIC ACIDS
When a carboxylic acid salt of calcium is heated, an aldehyde id formed. More
specially methanol is formed.
O
Ca(COO)2 heat CaCO3 + HCH

With other higher aldehydes, Ca salt of a carboxylic acid is heated with calcium
methanoate.

Examples:
(CH3COO)2 Ca(s) + (HCOO)2 Ca(s) heat 2CH3CHO + 2CaCO3
Ethanal

̅ )2Ca+ + (HCOO)2Ca heat 2CH3CH2CHO + 2CaCO3

(CH3 CH2 COO
Propanal

146
( ̅ )2 Ca+ + (HCOO)2 Ca heat 2
COO CHO + 2CaCO3
Benzaidehyde

Ketones can be prepared by heating Ca salts of higher carboxylic acids.

(CH3COO)2Ca heat CH3 CO CH3 + CaCO3

(CH3CH2COO)2Ca+ heat CH3CH2COCH2CH3 + CaCO3

Convert CH3CH2OH CH3COCH3

𝐸𝑥𝑐𝑒𝑠𝑠 𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72−

CH3CH2OH CH3COOH + Ca(OH)2
ℎ𝑒𝑎𝑡

(CH3COO)2Ca + H2O

CH3COCH3 heat

OZONOLYSIS
When an alkene is reacted with ozone, an ozonide id formed. When the ozonide
is diluted in H2O in presence of some zinc, a carbonyl compound is formed. Zinc
dust is used to decompose H2O2.

Note: Aldehydes formed depends on the types of alkene used. Symmetrical

alkene gives one type of aldehyde while unsymmetrical will give you both
carbonyls.
O
CH2 = CH2 + O3 CH2 CH2
O O

O O
CH2 CH2 H2O/Zn 2HCH + H2O2
O O

147
 O
CH3CH = CH2 + O3 CH3 CH CH2
O O

O
CH3 CH CH3 + H2O Zn CH3CHO + HCHO + H2O

O O

CH3
CH3 C = C – CH3 + O3 2CH3 CO CH3

CH3

CH3
CH3 C = CH CH3 + O3 CH3COCH3 + CH3CHO

The above method has the disadvantage of yielding a mixture of products which
may not be good in organic synthesis.

HYDROLYSIS (ACID) OF ALKYNES

When an alkyne is passed through hot H2SO4 in presence of mercury sulphate,
the carbonyl carbon is formed.

𝐻2 𝑆𝑂4 /𝐻𝑔 𝑆𝑂4

CH ≡ CH + H2O CH3CHO
60𝑜 𝐶
Ethanal

𝐻2 𝑆𝑂4 /𝐻𝑔 𝑆𝑂4

CH3C ≡ CH + H2O CH3COCH3
60𝑜 𝐶

HYDROGENATION OF ACID CHLORIDES

Acid chlorides are reduced by hydrogen in presence of catalysts like pd to form
aldehydes.

CH3COCl + H2 Pd CH3CHO + HCl

COCl + H2 Pd CHO + HCl

148
ACYLATION
Alkyl acylation is a reaction between acid halides with a benzene ring
compound. This reaction produces aromatic ketones when it is carried out in
presence of a halogen carrier (Al Cl3, FeCl3)

O
+ CH3COCl Al Cl3 CCH3 + HCl
Ethanoyl chloride
Phenyl ethanone

CH3 CH3 CH3

+ CH3COCl Al Cl3 COCH3 + HCl

COCH3

PHYSICAL PROPERTIES OF CARBONYL COMPOUNDS

Lower members of aldehydes and ketones are liquids and are miscible with H2O
forming neutral solutions. The miscibility in H2O is due to the polar carbonyl
carbon.

They have higher boiling points than their hydrocarbon counterparts. This is
because of the polar nature of the carbonyl carbon that results into the
intermolecular attractions but their boiling points are lower than those of
alcohols and carboxylic acids due to the lack of H2 bonding.

CHEMICAL PROPERTIES OF CARBONYL COMPOUNDS

Carbonyl compounds chemically react because of the property of the carbonyl
carbon which is a common functional group present in both aldehydes and
ketones.

A carbonyl carbon contains more electronegative oxygen bonded to carbon

which pulls electrons towards itself and attains a 𝛿 - charge while the carbon
remains 𝛿 +. Therefore, the carbon oxygen bond is polarised creating a good
condition for nucleophillic reagents to be added across the carbonyl carbon. The
intermediate formed with a negative on oxygen reacts with an electrophille to
form the final end product.

149
 𝛿+C = 𝑂𝛿−

𝑂𝛿− 𝑂̅: +𝐸

C C C
𝛿+ Nu Nu

:Nu

Carbonyl group in aldehyde is more reactive than in ketones.

Explanation:
In ketones, the presence of two alkyl groups having a positive inductive effect
highly neutralizes the positive charge in the carbon resulting into a less attraction
of a nucleophile.

𝑂𝛿− 𝑂𝛿−
R–C–H R–C–R
𝛿+ 𝛿+

Methanol is more reactive than other aldehydes. Explain.

In methanol only, hydrogen is bonded to the carbonyl carbon that the partial
positive charge formed is not neutralized making methanol more reactive.

Therefore, the greater number of alkyl groups added to a carbonyl carbon, the les
the reaction due to the following reasons:
(i) The alkyl groups have got electron pushing (positive inductive) effect
which neutralizes the partial) positive charge on the carbon.
(ii) Several alkly groups will have a crowding effect preventing a nucleophile
from being attached to the carbon.

Order of the reactivity of the following:

O O O
H-C=O CH3C=O CH3C–CH3 CH3CH2-C-CH2CH3 C3H7CC3H7.
H H Neutralization Steric hinderance
of charges

150
When other atoms of a more electronegative effect are added next to the carbonyl
group, the reactivity of the carbonyl carbon compound increases. E.g. if a
hydrogen on the carbon atom next to the carbonyl group is replaced with a
halogen, the reactivity increases.

O 𝑂𝛿− 𝐶𝑙 𝑂𝛿−
CH3CH2 C – H CH3 CH – C – H CH3C – C – H
𝛿+ 𝛿+
Cl Cl

REACTION OF CARBONYL COMPOUNDS

GENERAL REACTION (BOTH KETONES AND ALDEHYDES)
(i) Reactions of alkyl groups:
Both aldehydes and ketones containing alpha hydrogen i.e. hydrogens on
the carbons next to be carbonyl group undergo halogenations reaction,
when reacted with a halogen to form substituted products. Substitution
proceeds until the alpha hydrogens are replaced.

O O
CH3 CH + Cl2 CH2Cl C – H + HCl

Cl2
O O
HCl + CCl CH Cl2 CHCl2 CH + HCl

O
CH3 C CH3 + Br2 CH2Br C CH3 + HBr
Br2
O
CBr3COCH3 Br2 CH Br2 C CH3 + HBr

O + Br2 O + HBr

Br

O
CH3COCH3 + 3Cl2 CCl3 CCH3 + 3HCl

151
 Cl
O + 2Cl2 O + 2HCl

Cl

(ii) Reactions due to carbonyl group:

Both aldehydes and ketones containing a carbonyl group undergo the
following reactions:
Reduction (Reaction with H2)
Aldehydes and ketones are reduced by H2 in presence of a suitable catalyst
e.g. Ni/150oC, pt/pd into primary and secondary alcohols respectively.

𝑁𝑖/150𝑜 𝐶
CH3CHO + H2 CH3CH2OH

𝑃𝑡
CH3COCH3 + H2 CH3 CH CH3
OH

O
𝑁𝑖/150𝑜 𝐶
+ H2 OH

Using reducing agents:

Similarly, strong reducing agents such as Aluminum, Na, Lithium
tetrahydride, Na/Ethanol can also be used to effect reduction.

𝐿𝑖 𝐴𝑙𝐻4
CH3COCH3 CH3CH(OH)CH3
𝐷𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

𝑁𝑎/𝐸𝑡ℎ𝑎𝑛𝑜𝑙
CH3CHO CH3CH2OH

Mechanism of reduction:
𝑃𝑡
H2 H+ + :𝐻−
𝐻+
𝑂̅:
𝑂𝛿−
OH
CH3 𝐶𝛿+ CH3 CH3 – C – CH CH3 – C – CH3

𝐻− : H H

152
Addition of HCN (hydrogen cyanide)
Both carbonyl compounds react with HCNs to form 2 hydroxyl nitrates or
cyanohydrins. The HCN is generated insitu from the reaction between NaCN
and Conc. H2SO4.
OH
CH3CHO + NaCN + H2SO4 CH3 CH CN
2-hydroxy propanitrile.

OH
𝐶𝑜𝑛𝑐.𝐻2 𝑆𝑂4 /𝑁𝑎𝐶𝐻
CH3 CO CH3 CH3 C CH
CN

CH3 CH3
CH3 CH CHO + KCN/H2SO4 CH3 CH CH CN
OH
O
C CH3 KCN/H2SO4 OH
H

CH3 CH3 OH
CH3 C CHO HCN CH3 C CH CN
CH3 CH3

Mechanism:
2KCN + H2SO4 2HCN + K2SO4

CH3 H CH3 H 𝐻𝛿+

CH3 CH – C = 𝑂𝛿− ̅:
CH3 CH – C - O
𝛿+ CN

:𝐶̅ ≡ 𝑁 CH3
CH3 CH CH C ≡ N
OH
2-hydroxyl, 3-methyl butanitrile.

153
REACTION WITH NaHSO3
Both carbonyl compounds react with a saturated solution of NaHSO3 to give
crystalline solids of NaHSO3 derivatives.

CH3 CHO + NaHSO3 CH3 CH S𝑂̅3Na+

(saturated) OH
Ethanal sodium hydrogen sulphite.

OH
CH3CO CH3 + NaHSO3 (CH3)2 C - S𝑂̅3Na+

O S𝑂̅3Na+
+ NaHSO3
OH

Mechanism:
NaHSO3 Na+ + H S𝑂̅3.

O CH3 O CH3 Proton shift O CH3

̅ - S:
:O 𝛿 +𝐶 = 𝑂𝛿− O = S – C - 𝑂̅ O = S – C – OH
OH CH3 OH CH3 ̅ CH3
O

O CH3 O
O = S – C – OH Na+ O=S – C – CH3
̅ CH3
O ONa CH3

ADDITION REACTION WITH PCl5.

Both carbonyl compounds react with PCl5 to give gem-dihalides with no
steaming in moist air i.e. (No hydrogen halide formed) which distinguishes
between alcohols and carbonyl compounds.

Cl
CH3 CHO + PCl5 CH3 CH + POCl3
Cl

154
 Cl

CH3 COCH3 + PCl5 CH3 C – CH3 + POCl3

Cl

CONDENSATION REACTIONS
Aldehydes and ketones react with compound containing amino groups to form
condensations products and loss of H2O molecule. These products formed have
got sharp melting points which are used in identification of the original
compounds.

These types of reactions are condensation because there is elimination of a H2O

molecule.

C = O + R – NH2 C = N – R + H2O.

CH3 C CH3 + R – NH2 CH3 C CH3 + H2O

O N-R

Reagents Product R – group

1. Hydroxyl amine Oxime
HO – NH2 C = N – OH -OH

2. Hydrazine Hydra zone

NH2 – NH2 C = N NH2 -NH2

3. Phenyl hydrazine Phenyl hydra zone

NH NH2 C = N NH NH

4. Semi carbazine Semi carbazone

NH2 NH CONH2 C = N – NHCONH2 NH – CONH2

5. 2, 4 dinitrophenyl 2, 4 dinitrophenyl
Hydrazine (Brady’s reagent) hydrazone
NO2N NHNH2 C = N NH NO2 O2N NH

NO2 NO2 NO2

155
Mechanism:
NHNH2 CH3
NO2
CH3COCH3 + H+ C = N NH NO2 + H2O

NO2 CH3 NO2

O
CH3 CH + HO – NH2 CH3 CH = N – OH + H2O.

O CH3
CH3 C CH3 + NH2 – NH2 C = N NH2 + H2O
CH3

O CH3
CH CH2 C CH3 + NH NH2 CH2 – C = NNH

CH3 CH2 CH2 CHO + NH2 NH CONH2 CH3CH2CH2 CH = N NHCONH2

Mechanisms of condensation reactions of carbonyl compounds

O
CH3 CH + HO – NH2 H+ CH3 CH = N – OH + H2O

O: O+H OH
CH3C – H H+ CH3C – H CH3C – H

HO - N̈H2 HO – N – H

H+ shift

156
CH3 C = NOH -H + CH3 – C – H -H2O +OH2

H HO −N
+ -H CH3 – C - H
Ethanal hydroxime
H – N:

O CH3
CH3 C CH3 + HO – NH2 H+ CH3 C = N – OH + H2O

O: OH OH
CH3 C – CH3 H+ CH3 C CH3 CH3 C CH3
HO – N̈H2 HO – N – H
H

Proton shift

CH3 CH3 OH2

CH3 C = N – OH H+ CH3 C =+ -H2O
N -H CH3 C – CH3
Propanone hydroxime
OH N:
H

O H
CH3 CH + H2N – NH2 CH3 C = NNH2 + H2O

𝑂𝛿− O H OH
H+
CH3 C – H CH3 C – N NH2 CH3 C – N̈ – NH2
𝑆ℎ𝑖𝑓𝑡
𝛿+
H H H H
H2 N N̈H2 -H2O
CH3 C – N – NH2

157
 O CH3
NH2 + CH3 CH C – H H+ CH3 CH C = N + H2O
CH3 H

O: OH
CH3 CH – C – H H+ CH3 CH C – H
CH3 CH3

N̈H2

H CH3 OH2 OH H
CH3 C =+
N
CH3 CH – C - N̈ – H CH3 CH CH – N

-H+ H CH3 H

CH3CH = N

Reactions with dilute NaOH

Aldehydes containing ∝-hydrogens and ketones react with dilute NaOH to form
hydroxyl alkanals or alkanones which are compounds containing both hydroxyl
group and carbonyl carbon but with doubling of the chain.

When these compounds are heated, H2O is lost and a double bond is formed.

2CH3 CHO ̅ H(𝑎𝑞)

O CH3 CH CH2 CHO

OH 2 hydroxy butane.

̅ H(𝑎𝑞)
2CH3CH2CHO O CH3 CH2 CH CH2CH2 CHO

OH

158
 O OH
2CH3 C CHO ̅ H(𝑎𝑞)
O CH3 C - CH2 C – CH3

CH3 O

Mechanism:
O O
CH2 – C – H C̅H2 C – H + H2O
H
̅H
:O

O CH3 ̅
O O
H C – CH2 𝛿 +C = 𝑂𝛿− CH3 CH – CH2 – C – H
H
+ H+ (H2O)
O
CH3 CH CH2 C – H
OH

Reactions with conc. NaOH

This reaction is possible only with aldehydes having ∝-hydrogens and not with
ketones to give brown resinious compounds formed by a series of condensation.

̅ H CH3 CH CH CHO
2CH3 CHO Conc. O –H2O CH3 CH = CH CHO
OH H

OH
CH3CH = CH CHO + CH3 CHO ̅H
O CH3 CH = CHCH – CH2 CHO

OH

CH3 CH = CH CH – CH2 CHO - H 2O CH3 CH = CH – CH = CHCHO

159
Polymerization:
̅ H CH3(CH = CH)n CHO.
i.e. nCH3CHO Conc. O

Reaction that distinguish between aldehydes and ketones.

Oxidation:
Aldehydes are oxidized by oxidizing agents e.g. H+(aq)/K2Cr2O7(aq) H+/CrO3 to
carboxylic acid.

Ketones are resistant to oxidation and therefore they never yield any product
with the same reagents.

Test:
Add 2 drops of an aldehyde into 2cm3 of H+(aq)/K2Cr2O7(aq) and warm.

An orange solution turns to green, the resultant solution becomes acidic.

CH3 CHO H+(aq)/Cr2𝑂72− (𝑎𝑞) CH3COOH + Cr3+(aq) + H2O.

Benedicts or Fehling’s solution:

Increases a solution containing Cu2+ ions. This solution is blue in colour but
when reacted with an aldehyde under heat, the aldehyde decreases Cu2+ to Cu+
resultant into a red-brown precipitate of Cu2O(s).

This property of aldehyde is reduction.

Ketones do not give a red-brown precipitate.

CH3CHO + Cu2+ + H2O heat CH3COOH + Cu2O(s).

Ammoniacal silver nitrate (Tollen’s reagents)

Ammoniacal silver nitrate solution is a solution of silver nitrate in NH3.

Aldehydes unlike ketones are oxidized by this mild oxidizing agent to a

carboxylic acid.

The Ag+ in the AgNO3 is reduced to Ag metals. Therefore, the observation made
in practicals is; a grey deposit or silvery coating on the sides of the test tube.

CH3 CHO + Ag (NH3)2 NO3 + H2O(l) heat ̅ NH4+ + Ag + NH4NO3.

CH3COO

160
Note that atmospheric O2 can also oxidize aldehydes. This is why samples of
aldehydes are normally contaminated when exposed to the atmosphere.

Iodoform / haloform reaction:

This reaction is only possible for methyl aldehydes and ketones. Since we have
only one methyl aldehyde, ethanal, the reaction is strictly positive for ethanol
and methyl ketones with the following structure.

Ethanal Methyl ketones

O
C C
H3C O CH3

The reaction is useful in practicals in determining the structure of carbonyl

compounds.

Test:
When iodine and NaOH is added to ethanol or a methyl ketone and warmed, a
yellow precipitate of tri iodo methane is formed.

CH3CHO + I2(g) + NaOH(aq) ̅ Na+ + H2O(l)

CHI3(s) + NaI + HCOO

O
CH3C CH3 + I2(aq) + NaOH(aq) warm CHI3 + CH3COONa+ + NaI(aq) + H2O.

CARNIZARO REACTIONS:
This reaction is only possible for aldehydes with out ∝-hydrogen ketones.

When NaOH is reacted with an aldehyde without an alpha-hydrogen of general

formula.

HCHO, CHO, the aldehyde is oxidized to carboxylic acid and the other

half is decreased to the alcohol.

2 CHO + NaOH COOH + CH2OH.

161
2HCHO NaOH HCOOH + CH3OH.

Name the reagent that can be used to distinguish between the following pairs of
compounds and in each case, state what would be observed when the reagent it
separately treated with each compound.

(i) COCH3 and COCH2CH3.

Reagent: Hot iodine solution in aqueous sodium hydroxide.

With COCH3 : A yellow precipitate.

With COCH2CH3 : No observable change.

(ii) CH3COCH3 and HCHO

Reagent:
With CH3COCH3
With HCHO

(iii) CHO and COCH2CH3

Reagent:
With CHO

With COCH2CH3

(iv) CH3CH2COCH3 and HCHO

Reagent:
With CH3 CH2 CO CH2 CH3
With HCHO

162
 CARBOXYLIC ACIDS
CARBOXYLIC ACIDS/ALKANOIC ACIDS

Carboxyclic acids are organic compounds with a general formula, O

R C – OH
(CnH2nO2) if they are saturated. They contain two functional groups:
O Carbonyl carbon group Carboxylic acid group
C O
- OH – hydroxyl group C–O–H

Carboxylic acids can be roughly categorized into the following:

(i) Monobasic acid:
Contains a single carboxylic acid group.
O
R C – OH

(ii) Diabasic acid

Contains two carboxylic acid groups joined to the same carbon chain.
O
HO – C – R – C – OH
O

(iii) Tribasic acid

Contains three carboxylic acid groups joined to the same carbon chain.
O O
HO – C – R – C – OH
C – OH
O

Nature of the alkyl group

Saturated carboxylic acid
Contains the R group with single carbon-carbon bond.
H H O
H – C – C – C – OH
H H
Alky group.

163
Unsaturated carboxylic acid
Contains at least a double bond in the alkyl chain.
O
H2C = CHC – OH Propenoic
Alkyl group.

NOMENCLATURE
According to the IUPAC system, carboxylic acids are named after their
corresponding alkanes. This is usually done by replacing a suffix-ane by oic.

HCOOH Methanoic acid

CH3COOH Ethanoic acid

CH3CH COOH 2-methyl propan-1-oic

CH3

COOH Benzoic acid

COOH 3-hydroxy benzoic acid

OH

CH3CH = CH CHOO Buten-2-oic acid

CH2 COOH 2-phenyl ethanoic acid.

HOOC-CH-COOH
COOH Butane-1, 2, 3-trioc acid.

CH3(CH2)4 CH = CH – (CH2)2 COOH Dec-4-enoic acid.

164
MONOBASIC CARBOXYLIC ACIDS
These contain a single carboxylic acid group. They are largely found in nature.
E.g.
Citric acid – in citrus fruits
Lactic acid CH CH COOH
OH
Formic acid (HCOOH) – insect bites.

ISOMERISM
Monobasic acids show both structural and functional isomerism.

STRUCTURAL
Chain isomerism:
Isomers differ from nature of the carbon chain C5H10O2.

CH3CH2CH2CH2COOH - Pentanoic acid

CH3 CH2 CH COOH - 3-methyl butanoic acid

CH3

CH3 CH CH2 COOH - 2-methyl butanoic acid

CH3

CH3
H3 C – C – COOH - 2, 2-dimethy propanoic acid
CH3

FUNCTIONAL
Monocarboxylic acids are isomeric with esters e.g. C3H6O2

CH3 CH2 COOH O

CH3 C O CH3
Propanoic acid Methyl ethanoate

165
 METHODS OF PREPARATION OF MONOCARBOXYLIC ACIDS

Monocarboxylic acids can be prepared from the following:

(i) Oxidation of primary alcohol and aldehydes:
Primary alcohols are oxidized by excess oxidizing agents until carboxylic
acids are formed. Aldehydes are also oxidized to carboxylic acids.

𝐸𝑥𝑐𝑒𝑠𝑠 𝑜𝑥𝑖𝑑𝑖𝑠𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡

Primary alcohol carboxylic acid
ℎ𝑒𝑎𝑡

𝑜𝑥𝑖𝑑𝑖𝑠𝑖𝑛𝑔
Aldehydes carboxylic acid
𝑎𝑔𝑒𝑛𝑡/ℎ𝑒𝑎𝑡

The main lab. Oxidizing agents used in this case are acidified
K2/Na2Cr2O7/ H+(aq) / CrO3(aq), H+(aq) / KMnO4(aq)

𝐸𝑥𝑐𝑒𝑠𝑠
𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72− (𝑎𝑞)
CH3 CH2 OH CH3 COOH
ℎ𝑒𝑎𝑡

𝐻 + (𝑎𝑞)/𝐶𝑟2 𝑂72−
CH3 CHO CH3 COOH
ℎ𝑒𝑎𝑡

(ii) Hydrolysis of acid nitriles and acid amides with alkaline or acid.
When a nitrile is heated under reflux with mineral acid or alkali, an amide
is first formed which later is further hydrolyzed to a carboxylic acid.

𝐻 + /𝐻2 𝑂
CH3 C≡N O
𝑂̅𝐻/ 𝐻2 𝑂
CH3 C – NH2 H+/H2O
Ethanitrile Heat Ethanamide heat

CH3 COOH + NH2

O
𝐻 + /𝐻 𝑂
CH3 CH2 C NH2 2
CH3 CH2 COOH + NH3
ℎ𝑒𝑎𝑡
Propanamide
The usefulness of this reaction is, increase of the carbon chain of one
carbon. E.g.
Convert CH2 = CH2 CH3 CH2CH2 OH

HCl 𝐾𝐶𝑁/𝜖𝑡𝑂𝐻
CH2 = CH2 CH3 CH2Cl CH3 CH2 CN
ℎ𝑒𝑎𝑡

166
 𝐿𝑖𝐴𝑙𝐻4
CH3 CH2CH2OH CH3 CH2 COOH
𝐷𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

(iii) From dicarboxylic acids

When dicarboxylic acids are heated, they are decomposed by loss of CO2
to form a monocarboxylic acid. This reaction is important in reducing the
carbon chain by one carbon.

HOOCCOOH heat HCOOH + CO2

HOOCCH2 COOH heat CH3COOH + CO2

COOH COOH
160𝑜 𝐶
COOH + CO2
ℎ𝑒𝑎𝑡

PROPERTIES OF CARBOXYLIC ACIDS

Physical properties:
Lower members (C1 – C4) are colourless liquids very soluble in H2O.

Medium members (C5 – C9) are solids only partially soluble in H2O.

SOLUBILITY OF CARBOXYLIC ACIDS IN H2O.

Solubility of carboxylic acids decreases with the increase in the carbon chain.
This is because the more number of carbon chains which are hydrophobic
outweighs the carboxylic acid group, which is responsible for forming H2 bonds
with H2O hence low solubility.

Melting and boiling points:

Carboxylic acids show high values of melting and boiling points compared to
their corresponding alcohols and alkanes. This is because a single molecule of a
carboxylic acid dimerises via H2 bonds which makes their melting and boiling
points to be higher.

By them undergoing dimerization, their apparent molecular masses when

determined by cryoscopic method to be twice the actual molecular mass.

167
 O H-O
H3C – C C – CH3 Apparent Mw = 120
O–H O Dimes
2-hydrogen bonds Real Mw = 60

The formation of H2 bonds also make them to be very soluble in H2O.

CHEMICAL PROPERTIES
Acid nature:
Carboxylic acids are acidic in nature. They are more acidic than phenol but less
acidic compared to mineral acids. Aqueous solutions of carboxylic acids turn
litmus paper red.
When dissolved in H2O, they dissociate. An equation is established as shown.

O O
R – C – OH + H2O R C - 𝑂̅(𝑎𝑞) + H3O+(aq)

[𝑅𝐶𝑂𝑂̅] [𝐻3 𝑂+ ]
Ka =
[𝑅𝐶𝑂𝑂𝐻]
Moldm-3.

The Ka value is then used to denote the strength of the acid. The bigger the Ka
value, the stronger the acid.

Acid Ka PKa
Methanoic, HCOOH 1.77 x 10-4 mol dm-3 3.75
Ethanoic, CH3 COOH 1.75 x 10-5 mol dm-3 4.82

Another important value is PKa, therefore the higher the PKa value, the weaker
the acid.

Explanation/reason for acid strength

Acidity of carboxylic acids is determined by a number of factors;
(i) Resonance of the carboxylic ion
When the carboxylic acid group ionizes, it forms the carboxylic ion and
this ion may show several resonance structures in order to attain a more
stable form. The more stable the carboxylate, the stronger the acid.
O O ̅
O ̅
O
R–C R–C R–C R–C
OH ̅
O: O O

168
 I II III

I, II and III are resonance structures of carboxylic acid.

(ii) Inductive effect:

Inductive effect is a tendency of an atom or groups of atoms to donate or
withdraw electrons from a certain group.

Adjacent electron withdrawing substituents increase the acidity by further

stabilizing the carboxylate. E.g.
Acids Structure PKa
Ethanoic acid CH3CO2H 4.7
Fluoro ethanoic FCH2CO2H 2.6
Dichloro ethanoic ClCH2CO2H 1.3
Chloro ethanoic Cl2CHCO2H 2.9
Tri-chloro ethanoic Cl3CCO2H 0.9
Nitro ethanoic NO2CH2CO2H 1.7

The above table shows that the presence of an electron withdrawing atom
pulls electrons from the bond decreasing electron density of that bond
(O–H) and the ease of a proton release.

More atoms of such groups decrease the electron density of the O – H

bond further and stabilizing the carboxylate thus high acidity.

The data below shows the PKa of the following acids. Explain.
Acid PKa
CH3 COOH 4.7
CH3 CH2 COOH 4.9

REACTIONS OF CARBOXYLIC ACIDS

They react as weak acids.
They react with bases e.g. (KOH and NaOH) to form a salt and H2O.
169
 O O
R C – OH + NaOH R ̅ Na+
CO + H2O.

CH3CO2H + OH ̅ (aq) + H2O.

CH3COO

COOH ̅ K+
COO
+ KOH + H2O

REACTION WITH SODIUM CARBONATE (Na2CO3)

Carboxylic acids unlike phenol react with Na2CO3 very slowly to liberate CO2(g).
This reaction is of practical importance in distinguishing carboxylic acids from
phenols. The reagent used is saturated Na2CO3.

CH3COOH + Na2CO3(aq) 2CH3COONa+ + H2O(l) + CO2(g)

Similarly, CO2 can also be evolved from saturated NaHCO3.

COOH ̅ Na+
COO
+ NaHCO3(aq) + CO2(g) + H2O(l)

COOH ̅ Na+
COO
+ Na2CO3(aq) + H2O(l) + CO2(g)

OH CO2
3-hydroxy-benzoic ̅ Na+
COO
acid

OH

170
 OTHER REACTIONS:
With SOCl2.
Carboxylic acids react with SOCl2 in presence of an organic base e.g. pyridine to
form an acid chloride and SO2. This is one useful way of preparing acid
chlorides.

̅ 3𝑁
𝑡𝑡
RCOOH + SOCl2 O
𝑝𝑦𝑟𝑖𝑑𝑖𝑛𝑒
R – C – Cl + SO2(g) + HCl(g)

CH3COOH + SOCl2 Pyridine CH3COCl + SO2 + HCl

Mechanism:
O ̅
O
CH3 – C – OH CH3 C – O – H

C = S̈ - Cl Cl – S = O
Cl Cl

Reaction with PCl5.

Carboxylic acids react with PCl3 or PCl5 to form acid halides.

O O
R C – OH + PCl5 RT R C Cl + POCl3 + HCl

CH3 COOH + PCl5 CH3COCl + PO Cl2 + HCl

Reaction with alcohols

React with alcohols in presence of a mineral acid to form an ester under heat.
This is called esterification where an ester is formed by refluxing a carboxylic
acid and alcohol in presence of an acid catalyst.
To complete the reaction, one of the components either an acid or an alcohol has
to be in excess or to remove an ester at a certain interval once it is formed.

O O
𝐻 + (𝑎𝑞)
R – C OH + R – CH2OH R C O – CH2 – R + H2O(s)
ℎ𝑒𝑎𝑡

171
 𝐻+
CH3 COOH + CH3OH CH3 C O CH3 + H2O
ℎ𝑒𝑎𝑡
Methyl ethanoate

O
𝐻+
COOH + CH3CH2OH C – OCH2CH3 + H2O
ℎ𝑒𝑎𝑡
Ethyl benzoate

O
𝐻+
COOH + OH CO + H2O.
ℎ𝑒𝑎𝑡

Phenyl benzoate

The mechanism for this reaction depends on the catalyst used/base catalysed or
acid catalysed.

Acid catalyzed mechanism.

+
O: OH OH
CH3 COH H+ CH3 C – OH CH3 – C – OH
CH3ÖH CH3 O+ − H

Reagent

O O+ H :O :OH
CH3 C OCH3 CH3 – C – OCH3 CH3 C - +OH2 + H3O+
OCH3

Reaction with amides:

Carboxylic acids react with amides to form substituted amines. With amines,
they form amides.
O O
R C OH + R2NH R C – NR2 + H2O.

172
 O
CH3COOH + (CH3)2NH CH3 C N – CH3 + H2O
CH3

O
CH3 COOH + CH3NH2 CH3 C – NH CH3 + H2O

COOH O CH3
+ CH3 NH CH3 C – N – CH3

This reaction occurs because of the presence of a proton on the amine which are
substituted by the carboxylate.

Mechanism:
O O- O-
CH3 C OH CH3 C – OH CH3 C – ÖH H+
CH3 N̈H CH3 – N+ – H CH3 N CH3
CH3 CH3 CH3 N CH3

O- O
CH3 C – OH2 CH3 C – N (CH3)2
CH3 N – CH3

REDUCTION OF CARBOXYLIC ACIDS

Carboxylic acids are usually reduced by reducing agents e.g. LiAlH4/ether (THF)
to form aldehydes and later alcohols (primary).

Note: NaBH4 is not commonly used to decrease carboxylic acids because it’s less
reactive.

173
 𝐿𝑖 𝐴𝑙 𝐻4 𝐿𝑖 𝐴𝑙 𝐻4
CH3 COOH CH3CHO CH3 CH2 OH + H2O.
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟 𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

OR:
𝐸𝑥𝑐𝑒𝑠𝑠 𝐿𝑖 𝐴𝑙 𝐻4
CH3 COOH CH3 CH2 OH + H2O
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

REACTIONS WITH HALOGENS (∝- HALOGENATIONS)

Carboxylic acids can be halogenated at the carbon atom adjacent to the
carboxylic group when reacted with reagents like Br2, PCl5. This reaction
depends on the character of the carbonyl compound where the product of the
reaction known as ∝-bromo carboxylic acid, is converted to ∝-hydroxy or ∝-
amino carboxylic acid.

O O
CH3 C OH + Br2 PBr3 BrCH2- C – OH + HBr
∝-bromo ethanoic acid

O O
CH2 C OH + Br2 PBr3 CH C OH + HBr.
Br

DECARBOXYLATION
Carboxylic acids with a carbonyl group at the third position readily undergoes
thermal decarboxylation where CO2 is lost to form a simple alkane when heated
in the presence of dry soda lime.

COOH
𝐸𝑥
𝑁𝑎𝑂𝐻/𝐶𝑎𝑂(𝑠)
+ CO2 + Na2CO3
ℎ𝑒𝑎𝑡

𝐸𝑥
𝑁𝑎𝑂𝐻/𝐶𝑎𝑂(𝑠)
CH3COOH CH4 + CO2 + Na2CO3
ℎ𝑒𝑎𝑡

O O O
HO C – CH2 – C – OH heat CH3 C OH + CO2
Malonic acid
(Propane -1, 3-dioic)

174
Carboxylic acid derivatives
Esters O
R C – OR

Amides O
R C – NH2

Anhydrides O O
R C- OC – R.

Acid halides O
RC–X

ACID HALIDES
These are compounds derived from carboxylic acids by reacting an acid with a
halogen. The commonest examples are acid chlorides.

O
R C – X where x = halogen atom.

Nomenclature:
Acid chlorides are named by replacing the suffix –ic in acids with –oyl.

O
CH3 C Cl Ethanoyl chloride

O
C Cl Benzoyl chloride

O
CH3 CH C Cl 2-methyl propanoyl chloride
CH3

175
PREPARATION
i) Reacting carboxylic acids with phosphorous halides.
O
CH3COOH + PCl3 CH3C Cl + H3PO3

O
CH3COOH + PCl5 CH3 C Cl + HCl + POCl3

ii) Reaction of carboxylic acid with thionyl chloride

This reaction should occur in a fume cupboard due to evolution of toxic
acids or should occur in the presence of pyridine which absorbs.

O O = C – Cl
𝑃𝑦𝑟𝑖𝑑𝑖𝑛𝑒
COH + SOCl2 + HCl + SO2.
ℎ𝑒𝑎𝑡

PROPERTIES OF ACID HALIDES

Physical:
They are colourless volatile liquids with irritating smells. They fume easily in
moist air due to evolution of HCl gas.
Have low boiling points than the corresponding acids.

Chemical properties:
They undergo a number of reactions making them suitable for organic synthesis.

Hydrolysis using H2O.

Acid halides react with H2O to form their parent carboxylic acids.

O O
CH3 C Cl + H2O RT CH3 C – OH + HCl

O
C Cl + H2O COOH + HCl

Mechanism:

176
 O O- O
C – Cl C – Cl- C OH2

:OH2 OH2 -H+

O
C OH

Reaction with alcohols:

Acid halides react with alcohols to form esters.

O O
CH3 C Cl + CH3 OH CH3 CO CH3 + HCl

O O
C – Cl + CH3 CH2 OH C O CH2 CH3

Mechanism:
O
CH3 C – Cl
O O- O
HÖ CH3 CH3 C – Cl CH3 C – O+ - CH3

O+ H
H CH3

-H+

O
CH3 C O CH3

Reaction with NH3 and amines:

Acid chlorides react with NH3 to form amides. This reaction is responsible with
primary/secondary amines to form amides.

O O
̅ H2
C–O -H+ C OH

177
 O O
CH3 CH C Cl + NH3 CH3 CH C NH3 + HCl
CH3 CH3 2-methyl propanamide

O O
C Cl + NH3 C – NH2 + HCl

Benzanamide

O O
CH3 C Cl + CH3 NH2 CH3 C – NHCH3 + HCl

O CH3
CH3 C Cl + CH3 NHCH3 CH3 C N – CH3 + HCl
O N, N-dimethyl ethanamide.

Mechanism:
O O- O
CH3 C Cl CH3 C+ – Cl CH3 C N(CH3)2
HN̈ – CH3 H – N – CH3 H
CH3 CH3 -H+

CH3 C – N(CH3)
O

NH2 CO Cl H O
+ N–C + HCl

Phenyl benzanamide.

Reaction with benzene:

Acid halides react with benzene in presence of a hydrogen carrier.

O O
𝐹𝑒 𝐶𝑙3
+ CH3 C Cl C CH3 + HCl
ℎ𝑒𝑎𝑡

178
 O O
C – Cl Al Cl3 C + HCl
+

Mechanism:
O O
CH3 C – C Al Cl3 CH3 C+ (Al Cl4)-

O O
C+ CH3(Al Cl3)- C CH3
+ H + Al C𝑙4−

O
C𝑙4− + H+ Al Cl3 + HCl C CH3

AMIDES
Amides are compounds derived from carboxylic acid and nitrogen containing
compound like amine or NH3 with a general formula O
R C NH2.
Unlike amines, they contain a carbonyl carbon directly attached to the nitrogen.

Naturally, such compounds are found in proteins.

Nomenclature:
Amides are named as derivatives of parent hydrocarbons alkane, replacing – e –
amide.
E.g.
O
H C – NH2 Methanamide

O
CH3 C – NH2 Ethanamide

179
 O
C – NH2 Benzenamide

CH3CONH(CH3)2 N, N-dimethyl ethanamide

O CH3
CH3 CH2 C – N – CH3 N, N , N – trimethyl propanamide.
CH3

PROPERTIES OF AMIDES
Physical:
All amides are colourless crystalline solids except ethanamide. They have got
higher boiling points than corresponding carboxylic acids due to the formation of
H2 bonding.

PREPARATION
Reaction between acid halides and NH3 or amines.

O O
CH3 C Cl + NH3 CH3 C – NH2

O H
C Cl + CH3 CH2NH2 C – N CH2CH3
O H

Esters and ammonia

O O
CH3 C O CH3 + NH3 heat CH3 C NH2 + CH3 OH

Acid anhydrides and ammonia

O O O
CH3 C O – C CH3 + 2NH3 heat 2CH3 C O NH2 + H2O
Ethanoic acid anhydride.

180
Mechanism:
O :O-
CH3 C – O – CH3 CH3 C – OCH3

N̈H3 N+H3 CH3 C – N+H3 + ŌCH3

O
O H O
CH3 C – N+ - H CH3 C – NH2 + CH3OH

H
̅:
CH3 O

With anhydrides
O O :O- O
CH3 C – OC – CH3 CH3 C – O – C CH3

N̈H3 +NH3

O
[

CH3 C - 𝑁+𝐻3 + O
CH3 C – O-

O H O O
CH3 C – N – H CH3 C – NH2 + CH3 C – OH
H
O
̅:
CH3 C - O

Amides are reduced by reducing agents such as sodium tetrahydride borate,

LiAlH4.

181
 O CH3
CH3 CH C NH2 ∈tOH / Na CH3 CH CH2 NH2 + H2O
CH3
2-methyl propanamide 2-methyl propyl amide

Hydrolysis
Amides are hydrolysed in presence of a mineral acid or an alkali to form a
carboxylic acid.

For example:
O
̅𝐻
𝐻+ / O
CH3 CH2 C NH2 + H2O CH3CH2 COOH + 𝑁𝐻4+
ℎ𝑒𝑎𝑡

CH3 O CH3
𝐻+ / (𝑎𝑞)
CH3 CH C NH2 + H2O CH3 CH COOH + 𝑁𝐻4+
ℎ𝑒𝑎𝑡

For distributed amides, hydrolysis produces a carboxylic acid and on amine.

Example:
O
𝐻 𝑂/𝐻 +
CH3 C NH CH3 2
CH3COOH + CH3 NH2
ℎ𝑒𝑎𝑡
N-methyl ethanamide Primary amine
For trisubstituted.
̅H
O
CH3 CON (CH3)2 + H2O CH3COOH + NH(CH3)2
ℎ𝑒𝑎𝑡
N-N-dimethylethanamide Secondary amine.

ACID CATALYZED HYDROLYSIS (MECHANISMS)

1. O: +OH OH

CH3 C – NH2 H+ CH3 C – NH2 CH3 C – NH2

:OH2 O+
H H

-H +

182
 NH3 O+ −H OH OH

CH3 C – OH +
CH3 C - NH3 H3 C – N̈H2 H+
OH OH

O
CH3 C – OH

NH3 + H+ NH4+

+
2. O: OH

CH3 – C – NH – CH3 H+ CH3 C – N – CH3

H
:OH2

OH
CH3 – C – N CH3
H
OH
CH3 C – NCH3 O+
:OH H H H

OH

CH3N̈H + CH3 C
O–H
O
CH3 C OH + CH3 NH2

CH3 N̈H

183
 HOFFMAN’S DEGRADATION

When an amide is heated with Br2 and an alkali, a primary amine id produced
which is less than one carbon from the original amide; this reaction is known as
Hoffman’s degradation because it involves reduction of the carbon chain by one
carbon atom.

(i) O
𝐵𝑟2 /𝐾𝑂𝐻
CH3 C NH2 CH3NH2
ℎ𝑒𝑎𝑡

Equation:
O
CH3 C NH2 + Br2 + 4KOH(aq) heat CH3 NH2 + K2 CO3 + 2KBr + H2O.

(ii) O
𝐵𝑟2(𝑎𝑞) /4Ō𝐻(𝑎𝑞)
C – NH2 NH2 + 𝐶𝑂32− + 2H2O + 2𝐵𝑟 −
ℎ𝑒𝑎𝑡

Convert COOH to NH2

COOH NH2

PCl5 heat NaOH/Br2

COCl

NH2 CONH2

184
 ESTERS
Esters are derivatives of carboxylic acids. Are highly volatile compounds with a
fruity smell. They conform to a general formula: O
RC – O – R

NOMENCLATURE
Esters are named using their parent acid name but adding the suffix –ate.

O
CH3 C O CH3 - methyl ethanoate

O
CH3 CH2 C O CH3 - methyl propanoate

O
CH3 O C CH3 CH2 CH3 - methyl butanoate

O
CH3 C – O CH2 CH3 - ethyl methanoate

O
C – OCH3 - methyl benzoate

O
C–O - phenyl benzoate

Isomerism
Esters show structural isomerism and functional isomerism.
Functionally esters are isomeric with carboxylic acids.

C4H8O2
CH3CH2CH2COOH – Alcohol

185
 O
CH3CH2 C O CH3 - Ester

PREPARATION OF ESTERS
(i) Esterification:
From carboxylic acids and an alcohol. This reaction is catalyzed by a
mineral acid or an alkali.

O
H+
CH3 COOH + CH3OH CH3 C O CH3 + H2O
heat

OH O
H+
+ CH3 COOH O C CH3 + H2O
heat

Phenyl ethanoate

Mechanism:
+
O: OH OH
CH3 C OH H+ CH3 C – OH CH3 C – OH

CH3 ÖH +O

CH3 H

+
OH2 H+ ÖH
CH3 C – OH CH3 C – OH

OCH3 OCH3

+OH - H+ O
CH3 C – OCH3 CH3 C OCH3 + H+

186
From acid chlorides and acid anhydrides
When alcohols are reacted with acid chlorides or acid anhydrides, an ester is
formed.
O O
CH3 C Cl + CH3 OH CH3 C O CH3 + HCl

O O
CCl + CH3 CH2 OH C O CH2CH3 + HCl

O O O
CH3 C O C – CH3 + CH3OH CH3 C O CH3 + CH3 COOH
Ethanoic acid anhydride.

REACTIONS OF ESTERS
Esters undergo the following reactions:

i) Hydrolysis
Esters are hydrolyzed in presence of a mineral acid to a corresponding
carboxylic acid and alcohol.
O
𝐻 + /𝐻2 𝑂
CH3 C O CH2 CH3 CH3 COOH + CH3 OH
ℎ𝑒𝑎𝑡

O
𝐻+
C – O CH3 + H2O COOH + CH3OH
ℎ𝑒𝑎𝑡

NOTE:
Hydrolysis involves cleavage at O
R–C–O-R
The position of this cleavage is useful in radiolabelling to trace for the reaction
mechanisms.

Example:
O O
R C - 18 16
O − R + H2 O Rc− 16
OH + R− 18
OH

187
ii) Reduction
Esters are reduced with LiAlH4 in presence of ether to carboxylic acid and
the alcohol.

Example:
O
𝐿𝑖𝐴𝑙𝐻4
C – O CH2 CH3 CH3CH2OH + COOH
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

iii) Reaction with NH3

Esters react with NH3 to give amides and alcohols.

Example:
O O
CH3 CH2 C O CH3 + NH3 heat CH3 CH2 C – NH2 + CH3OH

O
COOCH3 + NH3 heat C NH2 + CH3OH.

iv) Reaction with primary amines

O
C O CH3 + CH3NH2 heat COOH + CH3NH CH3.

AMINES
These are compounds that are derived from ammonia base by replacing one
hydrogen with an amino group. They therefore have a general formula.
RCH2 – NH2.

The functional group of amines is – NH2 (amino group).

NOMENCLATURE
Amines are named as derivatives of alkanes by adding amine suffix to the stem
name.

188
CH3NH2 methyl amine
CH3CH2NH2 ethyl amine
CH3CH2CH2NH2 propyl amine
NH2 phenyl-amine (aniline)

CH2NH2 phenyl methyl amine

CLASSES OF AMINES
Amines are classified into four groups or four classes.
i) Primary amines
Is formed when only one hydrogen is replaced from the NH3.

CH3CH2NH2 Ethyl amine

NH2 Phenyl amine (primary aromatic)

ii) Secondary amines

Is formed when two hydrogens of NH3 are replaced by alkyl or anyl
groups.

(CH3)2NH Dimethyl amine or N-N-dimethyl amine

CH3NHCH2CH3 Ethyl methyl amine

NHCH3 Phenyl methyl amine

iii) Tertiary amines

Are formed when all the hydrogens in the NH3 are replaced by the alkyl
group.

(CH3)3N Trimethyl amine

(CH3)2NCH2CH3 Phenyl dimethyl amine.

189
iv) Quartenary amines
Are salts formed when the lone pair on the Nitrogen is donated to an alkyl
group.

+
(CH3)3 NCH3 Tetramethyl amine.

Isomerism
Amines exhibit all the three types of isomerism, chain, positional and functional.

Write all isomers of C4H11N.

1. CH3 CH2 CH2 CH2 NH2 n-butylamine

2. CH3 CH CH2 NH2 2-methyl propylamine

CH3

3. CH3
CH3 – C – NH2 2-amino-2-methyl propane.
CH3

4. CH3 CH2 CH CH3 2-amino butane

1 and 2 are chain isomers.

3 and 4 are position isomers.

H
5. CH3 CH2 N CH2 CH3 N-diethyl amine (functional)

6. CH3
CH3 N CH2 CH3 (Functional)

METHODS OF PREPARATION
From alkyl halides
When alkyl halides are heated with NH3 in a sealed tube at a temperature of
100oC, the reaction gives a mixture of amines. This method is not suitable for
producing a specific amine because of a mixture of amines.

190
Although the products produced may be controlled by using excess NH3 and at
the same time separating each product by functional distillation.

𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
CH3 CH2 Cl + NH3(l) CH3 CH2 NH2 + HCl.
100𝑜 𝐶
Primary

𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
CH3 CH2 NH2 + CH3 CH2 Cl (CH3CH2)2NH + HCl
100𝑜 𝐶
Secondary

𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
(CH3CH2)2NH + CH3CH2Cl (CH3CH2)3N + HCl
100𝑜 𝐶
Tertiary

NOTE:
When excess NH3 is used,

𝑠𝑒𝑎𝑙𝑒𝑑 𝑡𝑢𝑏𝑒
CH3 CH2 Cl + 𝐸𝑥𝑐𝑒𝑠𝑠
𝑁𝐻3 (𝑙) CH3 CH2 NH2 + HCl
100𝑜 𝐶

Mechanism:
Excess NH3
𝛿+ 𝛿-
+
H3 N: CH2 – Cl CH2 - N H3
CH3 CH3 CH3 CH2 NH2 + H+
-H+

H+ + Cl- HCl.

From alkyl cyanides

When an alkyl cyanide also known as a nitrile is reduced with reducing agents
such as LiAlH4 or NaBH4. Or simply sodium in an alcohol, dry ether a primary
amine is formed.

𝐿𝑖𝐴𝑙𝐻4
CH3 C ≡ N CH3 CH2 NH2
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
Ethanitrile

𝑁𝑎
CH3 CH2 CN CH3 CH2 CH2NH2
𝑒𝑡ℎ𝑎𝑛𝑜𝑙
Propanitrile

191
 𝐿𝑖𝐴𝑙𝐻4
CN CH2 NH2
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

Benzenitrile

From acid amides

When an acid amide is reduced using reducing agents like LiAlH4/dry ether,
primary amines are formed.

O
𝐿𝑖𝐴𝑙𝐻4
CH3 C NH2 CH3 CH2 NH2 + H2O
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

O
𝐿𝑖𝐴𝑙𝐻4
CH3 C – NHCH3 CH3 CH2 NHCH3
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

HOFFMAN’S DEGRADATION
When amines are reacted with Br2 in a solution of KOH or NaOH, a primary
amine is formed which is one carbonless from the parent amide. This reaction
shortens the chain by one carbon and it is known a Hoffman’s degradation.
O
CH3 C NH2 + Br2 + KOH heat CH3NH2 + KBr + K2CO3 + H2O

From nitro compounds

When a nitro compound preferably aromatic nitro compound is reacted with tin
in conc. HCl or LiAlH4/ether, aromatic amine is formed.

NO2 NH2 + H2O

𝐶𝑜𝑛𝑐.
𝑆𝑛/𝐻𝐶𝑙
ℎ𝑒𝑎𝑡
(𝑟𝑒𝑓𝑙𝑢𝑥)

𝐿𝑖𝐴𝑙𝐻4
NO2 NH2 + H2O
𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟

This method is suitable for preparing aromatic amines.

192
 HYDROLYSIS OF TERTIARY AND SECONDARY AMINES

This produces primary and secondary amines respectively. When they are
heated with mineralized acid H2O or a base.

H+
CH3 NH CH3 + H2O CH3OH + CH3 NH2
heat
Secondary Primary

H+
CH3 CH2N(CH3)2 + H2O CH3 CH2OH + CH3NHCH3
heat
Tertiary Secondary

H+
CH3CH2NHCH3 + OH CH3 CH2 NH2 + CH3OH
H2 O

Mechanism: (Base catalysed)

PHYSICAL PROPERTIES OF AMINES

i. Lower amines up to C2 are gases while those with C3 = C11 are liquids,
higher amines are solids at room temperature.
ii. Lower amines have got a fishy ammoniacal smell or odour.
iii. Boiling points of amines are higher than those of corresponding alkanes.
iv. Lower members are soluble in H2O but the solubility decreases with
increase in molecular weight.

Explanations for boiling points and solubility

Question:
Methyl amine CH3NH2 Molecular Boiling point oC
31 -7

CH3CH3 30 -89

Methyl amine boils at a high temperature than ethane because of the presence of
intramolecular hydrogen bonding which holds methylamine molecules together
in the liquid phase and difficult to escape to vapour phase during boiling and
more heat required to boil while in ethane, the weak Van der Waal’s forces are
easily broken and loss heat required to boil.

Comparing three classes of amines, primary amine boils at a higher temperature

than the secondary followed by tertiary.

193
Amine Molecular weight Boiling point oC
CH3 CH2 CH2 NH2 59 49

CH3 CH2 NH CH3 59 35

CH3 – N̈ – CH3 59 3.5

CH3

Primary amine forms atleast two intramolecular hydrogen bonding due to the
presence of more hydrogen atoms on the nitrogen and hence boiling at a higher
temperature.

The secondary amine forms only one hydrogen bond since it has only one
hydrogen in the nitrogen while the tertiary amine has not hydrogen on the
nitrogen and therefore forming no hydrogen bonding and ends boiling at the
lowest temperature.

Assignment (Research work)

Carboxylic acids boil at higher temperatures than alcohols which also boils at a
higher temperature than an amine and an alkane has the least boiling point.
Explain.

BASICITY OF AMINES
Amines are bases which form weak alkaline solutions when dissolved in H2O.
Such solutions turn litmus paper to blue.
The basic strength of an amine is determined by the extent of ionization denoted
as Kb. The greater the Kb value, the more basic the amine. The basic character of
an amine can be explained by the presence of lone pair of electrons on the
nitrogen atom which are always donated.
The more available these lone pair of electrons are, the more basic an amine is.
The availability of electrons on the nitrogen atom is determined by the atoms
that are bonded onto it.
Groups of atoms that have got positive inductive effect will push electrons
towards nitrogen making them available while those with negative inductive
effect will lower the electron density on the nitrogen atom making them less
available.
+
CH3 NH2 + H2O CH3 N H3 + OH

194
 + ̅ H]
[CH3 N H3 ][O
Kb =
[CH3 NH2 ]

Questions:
1. Methylamine is a stronger base than ammonia.
2. Phenylamine is a weaker base than methylamine.
3. Ethyl methylamine is a stronger base than trimethyl amine.

Trend:
Secondary amine Primary Tertiary ammonia

4. Amino benzene is a weaker base than aliphatic primary amine. Explain.

The final of Basicity will be;

Secondary Primary Tertiary Ammonia Aromatic

Being basic amines, they react with mineral acids to produce salts. These salts are
strong electrolytes because they fully get ionized and their pH is slightly less
than 7.

+
1. CH3CH2NH2 + HCl CH3 CH2 NH3 + Cl

+
CH3 CH2 NH3 Cl CH3CH2 N+H3 + C𝑙 −

+
CH3 CH2 NH3 + H2O CH3 CH2 NH2 + H3O+

Acidic

+
2. NH2 + HCl NH3 Cl

+ +
NH3 Cl NH3 + Cl

+
NH3 + H 2O NH2 + H3O+

195
REACTIONS OF AMINES
1. With nitrous acid:
Nitrous acid being liable is generated insitu. Primary amines react with
nitrous acid to form a colourless solution of alcohol and a colourless gas of
nitrogen.

CH3CH2NH2 NaNO2/Conc.HCl CH3CH2OH + N2(g) + H2O.

Secondary amines will produce a yellow oily substances known as nitroso
amines.
CH3CH2NH2 NaNO2/HCl CH3CH2-N-N=O
CH3
Ethyl methyl nitroso amine

(CH3CH2)2 NH NaNO2/HCl CH3CH2-N-N=O

CH3
Diethyl nitosoamine.

Tertiary amines when dissolved in HNO acid to form NH4NO2 which when
warmed forms a nitrosoamine and an alcohol by decomposition.

(CH3)3N NaNO2/Conc. HCl (CH3)3 N+H NO−

2
Trimethy ammonium nitrite.

+
(CH3)3 N 2 Warm (CH3)2N-N=O + CH3OH
H NO−
Diethyl nitrosoamine.

Aromatic primary amines react with nitrous acid giving different products
depending on the temperatures.

At temperatures below 10oC, aromatic primary amines with nitrous acid to form
diazonium salts.
NaNO2 /Conc.
HCl + −
NH2 N2 Cl
<10o C
Benzene diazonium chloride.

NaNO2 /HNO3
NH2 +
𝑁 ≡ 𝑁 𝑁𝑂3−
<10o C
Benzene diazonium nitrate.
196
 NaNO2 /Conc.H2 SO4
NH2 +
𝑁 ≡ 𝑁 𝐻𝑆𝑂4−
<10o C
Benzene diazonium hydrogen
sulphate.

At temperatures above ten (>10oC), the major product formed is a phenol.

NaNO2 /Conc.
HCl
NH2 OH + N2(g) + H2O(l)
<10o C

The above reaction is of practical importance in distinguishing the classes of

amines.

In summary:
i) 1o amines : Yield a colourless solution and effervescence of a
colourless gas.

ii) 2o amines : Yield a yellow oily substance which when phenol and
conc. H2SO4 is added and the mixture made alkaline.
This yields an intense blue colour.

iii) 3o amines : A yellow oily substance persists.

iv) Aromatic amine : A brightly coloured compound known as an azo

dye is produced when 2-napthol ( OH) is
added.

2. Reactions with acid chlorides and acid anhydrides.

1o and 2o amines react with acid chlorides and acid anhydrides to form
amides.
O O
CH3CH2CH2NH2 + CH3 C Cl CH3CH2NH C CH3 + HCl

197
 O O
NH2 + CH3 C Cl NH C CH3 + HCl

O O O O
NH2 + CH3 C O C CH3 Pyridine NH C CH3 + CH3 C OH

Mechanism:

O O- O H
CH3 C Cl CH3 C – Cl CH3 C - +N
N̈H2 H–N–H H

-H +

O H
CH3 C – N

3. Reactions with sodium metal

Amines react with Na when heated to produce H2. This reaction is only
possible with 1o and 2o amines which do have H2. The tertiary ones
without H2 do not.

CH3 CH2 NH2 + Na heat CH3 CH2 NH Na + ½ H2

(CH3CH2)2NH + Na heat CH3CH2 Na + ½ H2

4. Reactions with alkyl halides

Aromatic and alkyl amines react with alky halides to form higher amines.

CH3NH2 + CHCl NH3NHCH3 + HCl

CH3NHCH3 + CH3 CH2 Cl (CH3)2N CH2 CH3 + HCl

198
 NH2 + CH3Cl NH CH3 + HCl

NHCH3 + CH3 CH2Cl CH2 CH3

N CH3 + HCl

DIAZONIUM SALTS
These are salts formed from primary aromatic amine when reacted with an
inorganic mineral acid. The process of forming these salts is diazotization.

Temperature is critical in the formation of a diazonium salt and the temperature

always has to be <10oC. Where X is the halogen or NO− 3 , HSO4 .
−

+ −
𝑁2 𝑋
Benzene diazonium chloride.

𝑁𝑎𝑁𝑂2
𝐶𝑜𝑛𝑐.𝐻𝐶𝑙 +
NH2 N≡ NCl−
<10𝑜 𝐶

What determines the anion is the acid used.

Nomenclature
Diazonium salts are named as benzene diazonium.

+
N≡ NCl−
Benzene diazonium chloride.

H3C −
𝑁≡ 𝑁𝐶𝑙 − 4-methyl benzene diazonium chloride.

+
N≡ NCl− 2-nitro benzene diazonium chloride.

NO2

199
 +
H3C N≡ NNO−
3 - 4-methyl-2-nitro-benzene
Diazonium nitrate.
NO2

+
N≡ NNO−
3

H3C 3, 5-dimethyl benzene diazonium

Hydrogen sulphate.
CH3

Physical properties of diazonium salts

Are a colourless crystalline solids which turn brown on exposure to air.

Their solutions are neutral to litmus but very soluble in H2O to give an ionic
solution that has got good electrolytic conductivity.

Chemical reactions
Diazonium salts are very useful in organic synthesis reacting with different
substances to form different products.

Coupling reaction
Benzene diazonium salts react with phenols to form brightly coloured
compounds known as azo compounds by adding an aromatic ring to the
nitronium ion a reaction known as coupling.

Ar – N = N – Ar or N=N

Azo compounds.

For coupling to occur, the aromatic ring must have a strong electron releasing
groups such as hydroxyl, NH2 – (amino), OR group and NHR group.

These groups will activate the ring making the electrons available at the para
position for diazotization.

If the para position is already occupied, then diazoti-phenol.

200
 OH + + −
𝑁2 𝐶𝑙 HO N=N + HCl

Phenyl amine p-hydroxyl azo compound

+
NH2 + N≡ NCl− H 2N N=N + HCl

p-amino azo compound.

2-naphol HO (Bright red solid)

+
OH + N≡ NCl −
N=N + HCl

2-napthol azo compound.

CH3 CH3
+
+ N≡ NCl −
N=N

CH3 CH3
1, 4-dimethyl benzene.

The importance of coupling

i) Test for primary aromatic amines:
If a primary aromatic amine is treated with a mixture of NaNO2 and HCl,
2-napthol, a bright red solid is formed due to the reaction of diazonium
salt with 2-napthol at a temperature below 10oC.

ii) It is used in preparation of dyes (coloured compounds) e.g. methyl orange

indicator is prepared by coupling 4-hydrogen sulphite benzene, diazonium
chloride and dimethyl phenyl amine.

+
HO3S N≡ NCl− + N(CH3)2
HO3S N=N N(CH3)2 + HCl
Methyl orange.

F OH N=N OH
heat
+
N2BF4 N≡ NCl− NaO+

201
 HBF4 H3PO2

𝐻 + /𝐻2 𝑂
OH
ℎ𝑒𝑎𝑡
CuBr/HBr O
𝐻 + /𝐻2 𝑂
Br CuCN CN CNH2 NH2
ℎ𝑒𝑎𝑡
CuCl/HCl Br2/KOH
Cl

Convert Nitro benzene to chloro benzene

NO2 Cl

Heat 𝑆𝑛/𝐶𝑜𝑛𝑐.
𝐻𝐶𝑙

NH2

NaNO2/Conc.HCl CuCl/HCl
Warm
<10oC

+
N≡ NCl−

APPLIED ORGANIC CHEMISTRY

1. Polymers (plastic)
2. Lipids – Soap and detergents
3. Hydro carbon – petroleum

POLYMER AND POLYMERISATION

202
Definition:
A polymer is a compound of high molecular mass made up of small repeated
units known as monomers. These molecules are formed by a process known as
polymerization.

Polymerization is process of combining low molecular weight molecules

repeatedly in some regular manner to form a high molecular mass compound. In
polymerization, the low molecular mass molecules are always known as
monomers.

These are simple molecules which when combined can form a dimer, trimer or a
polymer when many.

POLYMERS:
There are two types of polymers depending on how they are formed.

i) Natural polymers
Are naturally occurring polymers not made by man e.g. cotton, wool,
protein, rubber, starch e.t.c.

ii) Artificial polymers (Synthetic)

These are man-made polymers.
Example: Polythene Poly vinyl chloride (PVC)
Polyester Terylene
Nylon e.t.c.

Advantages of synthetic polymers over natural

- They can be produced in large quantities within a short period of time.
- Are recyclable
- Have got improved properties e.g. cross linkages for toughness, high
density for tensile strain.

Advantages of natural polymers over artificial polymers

- They are biodegradable
- They are cheap since no process involved in producing them.

Properties of polymers
A polymer is judged by some of these properties:
i) The length of a polymer

203
 This determines its strength and the melting point. The longer the length,
the stronger the polymer would be and a high melting point it will have.

ii) Cross linkages

A cross link is a force that joins molecules within a polymer. When a
polymer has got several cross linkages, it will have an increased strength.

iii) Branching
Increased branches within a polymer decreases its strength and lowers its
melting point.

iv) Intermolecular forces

If a polymer has got several intermolecular forces within itself, then it will
have increased strength than when there are few intermolecular forces.

CLASSIFICATION OF POLYMER

There are several ways of classifying polymers:

i) Addition polymers
These are polymers made by directly adding monomers without loss of
any simple molecule.
Example:

n CH2 = CH2 + CH2 = CH2 CH2 – CH2 n

(ethene) Polymer (Polythene)

ii) Condensation polymers

These are polymers made by combining monomer units but splitting out a
small molecule which is usually H2O. E.g. Terylene
PET (Polythene terathalein)

iii) Thermoplastic polymers

These are polymers that can soften and flow when heated and harden
when they cool. In other words, they can be remolded into any shape by
heat. E.g. polythene.

iv) Thermosetting polymers

204
 these are polymers which when heated cannot melt but instead burn away.
Such polymers cannot be remolded since they are initially set to a solid.
E.g. Formica.

Other terminologies include:

i) Copolymer
A copolymer is a type of polymer made by having one or more different
monomers. E.g. SBR (Styrene Butadiene Rubber). This is made from
styrene and buta-1, 3-diene.

ii) A fibre
Is a form of polymer consisting of strings or bundles of strings that settle
up during its formation.

iii) Elastomers
Is a type of polymer which when stress is applied, and released, it springs
back to its original position e.g. rubber.

ADDITION POLYMERIZATION
Addition polymers
Definition: Addition polymerization

Examples:
Monomers Formula Polymer and trade Uses
name
Ethene CH2 = CH2 Polythene Making bags, squeeze
(ethylene) (Polyethylene) bottles, films, toys,
moulded objects,
shoes, electrical
insulators e.t.c.
Propene CH3CH = CH2 Poly propene Making bottles, films,
(propylene) (polypropylene) indoor and outdoor
(Vectra) carpets.

Polypropene is formed when propene is heated at various pressures and catalytic

temperatures.

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 ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒𝑠
CH3CH = CH2 + CH3CH = CH2 𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡 CH3
ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

CH - CH2 n
(Polypropene)

Vinyl chloride CH2 = CHCl Poly vinyl - Making of floor

(Chloroethene) chloride (PVC) tiles.
- Making pipes,
raincoats,
insulator tapes.

By modifying ethene, several polymers with better properties can be formed by

adding groups of atoms with either –OH group (polar) or (non -polar, giving
polymers such as poly viny alcohol and polystyrene respectively. i.e.

OH OH
ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒/ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
n CH2 = CH CH2 – CH n
𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
(Poly viny alcohol) [PVA]

ℎ𝑖𝑔ℎ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒/ℎ𝑖𝑔ℎ 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

nCH2 = CH2 CH2 – CH
𝑐𝑎𝑡𝑎𝑙𝑦𝑠𝑡
n
Polystyrene (PS)

Styrene CH2 = CH Polystyrene Making food and drink

(Styre form) or containers, coolers,
styrone construction materials,
mattresses e.t.c.
Acryonitrile CH2 = CHCN Polyacrylonitrile Fabrics, rugs e.t.c.
(Acrilan)
Vinyl acetate CH2 = CHOCOCH3 Poly vinyl Latex paint, coatings,
acetate (PVA) textiles, adhesives.

Emphasis: Structure of the polymer and its monomer.

1. H Cl OCOCH3
CH – C – CH – C

206
 Cl OCOCH3 H n
Polymer

Rules of writing monomers from polymers

Examine whether you are going to see the repeating units.

CH = CHOCOCH3 (Monomer)

2. CH2 – CH = C – CH2
CH3 n
Polymer

Monomer
CH2 = CH C = CH2 (2-methyl buta-1, 3-diene)

CH3

HIGH DENSITY POLYTHENE AND LOW-DENSITY POLYTHENE (HDPE &

LDPE)

On the other hand, if ethene is polymerized giving branches, it will end up

producing a low density polymer of 0.92g/mc and this polymer will be known
as LDPE which is soft and flexible.

CONDENSATION POLYMERS
These are formed by splitting monomers to eliminate a small molecule which is
usually H2O. This reaction is known as condensation reaction.

The empirical formula of the polymer in condensation polymerization is not the

same as that of a monomer.

Example:
i) Polyester (Dacron)

207
 Are formed by reacting a carboxylic acid and an alcohol monomers to form
a polyester and H2O molecule. E.g.
Benzene-1, 4-dioic (Terathepthalic acid) and Ethane-1, 2-diol.

O O O O
n HO–C C OH + HO – CH2 CH2 OH O C C – O CH2 – CH2 n + H2O

Uses of polyesters
- Used in making of textile fabrics.
- Making films, magnetic coated films using audio and video tapes.
- In heart/cardiac operations to replace some heart blood vessels because it is
non toxic, inert and non inflammatory.

Other examples:
O O O O
C C – Cl + n HO CH2CH2OH Cl C C – Cl-
Cl

O O Cl
O C C – O – CH – CH2 n O Polymer

Monomer

O O
HO – C C – OH and Cl CH CH2 OH
OH

Polymer
O O
C C – CH2 C – O – CH2 – CH – CH2 nO

Monomer

O O
HO C CH2 C – OH and HO CH2 CH CH2OH
208
Papan-, 3-dioic

2-phenyl propane -1, 3-diol.

ii) Lactic acid (2-hydroxy propanoic acid) polymer

Is a polymer made up of one monomer of 2-dydroxy propanoic acid which
undergoes self condensation. The uses of this polymer are of great
importance in surgery and stitching broken deep wounds.

The advantage is that the polymer threads get dissolved in the body.

O O
n CH3 CH – COOH O – CH – C O + H2O
CH3 n

O
O – C – C – O H . HO OC – CH CH3
CH3 O H
HO OC – CH – CH3

OH

O O O
O C – CH – O – C – CH – O – C – CH OH
CH3 CH3 CH3 n

iii) Polyamides
These re polymers formed by condensing a dicarboxylic acid or carboxylic
acid chloride with a diamine to form an amide bond or link.

Examples:
Ethane -1, 4-dicarboxylic acid
Hexane -1, 6-diamine
Ethane-1, 2- dioic
OO
H2N-(CH2)4 NH2 + HO C C – OH

209
 H H O O
N – (CH2)4 – N – C – C n O + H2O

Peptide or amide bond.

Other examples
i) Nylon-6 6:
Is a polymer of Hexane-1, 6-dioic or its acid chloride and Hexane-1, 6-
diamine. It is called so because its monomers are made up of 6 carbon
atoms each.

O O
H2N – CH2(CH2)4 CH2 – NH2 + HOC-(CH2)4 C – OH

O O
Cl – C – (CH2)4 C – Cl

H H O O

N – CH2(CH2)4CH2 – N – C – (CH2)4 – C nO

Uses:
- Made of high quality fabric for the making of clothes.
- Used in parachutes.
- Used in military gear.
The advantage of nylon-6, 6 is that it has got a good tensile strength, H2O
repellant, however, it has got a disadvantage of burning easily when put
on fire.

Polymer

O O H H

210
 O C – CH = CH – C – N – CH CH2 - N
n

Monomer
O O
HO – C CH = CH C – OH and H2N(CH2)2 NH2
But-2-ene-1, 4-dioic Ethane-1, 2-diamine

Polymer

O
O C – CH – C – N – CH – N
O CN H H n

O
HO C – CH – C – OH and H2N – CH – NH2
O CN
2-cyanopropane-1, 3-dioic 2-pl

NATURAL POLYMERS
These are polymers not made by man.

Examples:
Cotton
Wool (Polyamides)
Proteins
Carbohydrates (Polysaccharide)
Lipids (Polyesters)
Rubber

RUBBER

211
NATURAL RUBBER
Is a polymer of 2-methyl buta-1, 3-diene which is simply known as isoprene unit.

Natural rubber is obtained from the rubber tree. Naturally, the rubber tree
polymerizes the isoprene units by linking carbon 1 and carbon 4 and this leaves a
double bond between carbon 2 and carbon 3 which double bond is in a cis –
configuration.

CH3 CH3
C CH2 + C CH2
H 2C C H2C C
H H

CH3 CH3
C CH2 C CH2

CH2 C CH2 CH
n
Rubber
OR:
CH3
H2C – C = C – CH2
H n

Natural rubber is weak due to a few cross linkages and therefore it is less elastic
but it can be improved by the process called Vulcanization.

Definition:
Vulcanization is a process of making rubber, hard, tough and resistant to
wearing so that it is made useful. This is done by cross linking monomers using
disulphide bonds, S-S-bridge linkage.

When rubber is heated with sulphur, it forms S-S linkages which make it tough.
Natural rubber
CH3 H
CH2 C

212
 CH2 C CH2
C=C CH2
CH2

+S

CH3 H CH2 CH3 H

C – C – CH2 C
CH2 C CH2

S S S S

S S S S
CH2
C C CH2 C C

CH2 CH3 H CH CH3 H

Vulcanized rubber

Vulcanized rubber is useful in the following ways:

- Manufacturing of carlyres
- Manufacture of balls, bags, shoe soles e.t.c.
- Used ion insulation e.t.c.

Synthetic rubber
The knowledge of composition and structure of rubber has given rise to synthetic
rubber. This has made polymer by polymerizing elastomers to give rise to a
copolymer which has got some properties of natural rubber.

One of the examples is:

Stfren buta-diene rubber (SBR) which is made by polymerizing buta-1, 3-diene
and styrene.

n CH2 = CH CH = CH2 + n CH = CH2

buta -1, 3-diene Phenyl ethene

213
 CH2 – CH = CH – CH2 – CH – CH2 n

FATS AND OILS

- Triglycerides / trimesters
- Differences between the oils and fats
- Components of a triglyceride (glycerol and fatty acid)
- Saponification
- Additives of soap
- Properties of soap.

FATS AND OILS

Fats and oil are trimesters made from glycerol (propane-1, 2, 3-triol) and long
chain carboxylic acids called fatty acids. The R – groups of the acids, which can
be the same or different within the same molecule, can be saturated or
unsaturated, i.e. they may contain one or more carbon-carbon double bonds.

COMMON FATTY ACIDS

Name Number of carbon atoms Formula
Saturated acids
Butanoic C4 CH3CH2CH2CO2H
Lauric C12 CH3(CH2)10CO2H
Myristic C14 CH3(CH2)12CO2H
Palmitic C16 CH3(CH2)14CO2H
Stearic C18 CH3(CH2)16CO2H

Unsaturated acids
Oleic C18 CH3(CH2)7CH=CH(CH2)7CO2H
Linolenic C18 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7CO2H

A fatty acid – R group may be unsaturated, monounsaturated or

polyunsaturated, depending on whether one or more double bonds is present.

214
 O
CH2 – OH CH2 – O – C - R
O O
CH – OH + 3RC – OH CH – O – C – R + 3H2O
O
CH2 – OH CH2 – O – C – R
Glycerol Fatty acid Fat or oil

TRIGLYCERIDES (Triesters)
Common fats and oils made of a glycerol and fatty acids (act as components).
Triglycerides consist of three fatty acids and one glycerol.

FATTY ACIDS AND GLYCEROL

(Components of a triglyceride)

GLYCEROL
Is a polyhydric alcohol made up of three carbon atoms and 3 hydroxyl groups. It
is therefore a small molecule.

OH H H H
HO CH2 – CH – CH2OH Or H–C–C–C-H
OH OH OH
Glycerol

FATTY ACIDS
A fatty acid is a long carbon chain molecule consisting of a carboxylic acid group
at one end. The long carbon chain makes it to be hydrophobic and the carboxylic
acid group makes it to be hydrophilic.

i.e. CH2 CH2 CH2 COOH Hydrophilic group

H3C CH2 CH2 CH2

Hydrophobic tail (group)

If there are no double bond in the hydrocarbon chain, then the fatty acid is said
to be saturated fatty acid.
Example: Stearic acid (Octadecanoic acid)
215
 CH3(CH2)16COOH

Started fatty acids from straight chains and their physical state is largely solid at
room temperature because of their high melting points.

On the other hand, fatty acids that have got one or more double bonds within the
hydrocarbon chain are said to be unsaturated fatty acids.

Example:
Oleic acid (Octadec-cis-a-enoic acid)
C18 – [CH3(CH2)7CH = CH(CH2)7CO2H]

CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2

H3C CH2 CH2 CH2 CH CH CH2 CH2 CH2 COOH

The presence of a double bond in the hydrocarbon chain results into the
formation of a bend, which prevents the molecules from close packing resulting
into the fatty acids having low melting points.

Those with trans double bond will tend to have fairly straight or linear carbon
chain and the molecules will closely pack easily with high melting points making
them solids at room temperature.

Fatty acids with more than one double bond are called polyunsaturated fatty
acids (PUFAS).

Example: Linolenic acid – C18.

CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7CO2H

SPONIFICATION

216
Saponification is the process of making soap.

SOAPS AND DETERGENTS

SOAP
Soap is sodium or potassium salt of long chain carboxylic acids obtained by
boiling fat or oil with NaOH or KOH solution.

MANUFACTURE OF SOAP
Oil or fat is put on a pan, sodium hydroxide solution is added and the mixture
boiled.

Sodium chloride (Common salt) is added to precipitate out the soap a process
known as salting out. Soap precipitates out as a hard cake.

It is then removed and processed into various shapes. Perfumes and dyes are
also added to add value to the soap.

O
CH2 – O – C – R CH2 – O – H
O O
CH – O – C – R + 3NaOH CH – O – H + ̅ N𝑎+
3R C - O
O
CH2 – O – C – R CH2 – O – H Sodium stearate
Glycerol/stearate Glycrol (Soap)
(a fat)
R = (CH2)16CH3

SOURCES OF OILS
i) Vegetable oils:
These can be obtained from cotton seeds, sunflower, simsim, castor,
groundnuts e.t.c.

In extraction of vegetable oil after removing the husks, the seeds are then
crushed in power form and then boiled with H2O for some time. The oil
floats on top of the H2O.

ii) Animal oil:

These are esters obtained from animals e.g. from whale, fish (sardines) and
lard oil.
217
SOURCES OF FATS:
i) Vegetable fats:
Are obtained from plants like coconut or palm trees.

ii) Animal fats:

Are obtained from animals e.g. butter from milk and lard.

Uses of fats and oils

- Are used for food.
- In the manufacture of soap, candles and hair oils.
- In the manufacture of paints and vanishes.
- Ground nut oil is used to make vegetable ghee.

DISADVANTAGES OF USING ORDINARY SOAP

Soap forms scum with hard H2O. Hard H2O contains dissolved Ca2+ or Mg2+
which reacts with soap forming insoluble Ca2+ salt called scum.

O
2 R C ONa(aq) + Ca2+ ̅ )2Ca2+(s) + 2Na+(aq)
(RCOO

O
2 C17H35 C ONa(aq) + Ca2+(aq) (C17H35COO)2Ca2+(s) + 2Na+(aq)

Formation of scum is expensive in that much soap has to be used to produce

enough later for washing.

It also stains clothes.

THE CLEANING ACTION OF SOAP

A molecule of soap contains a water loving part which is polar COO ̅ called
hydrophilic part and the non polar ware insoluble (dirt soluble) part R – CH2
called the hydrophobic part.

During washing, these molecules are dispersed and they form a spherical cluster
around grease or dirt called micelle with the polar end attracted by H2O. The dirt
combines with the hydrophobic part while H2O dissolves in the hydrophilic part.

218
As H2O molecules attract the polar end, the surface tension of H2O is lowered.
Repulsion between the polar end of soap and rinsing help remove the dirt.

DETERGENTS
Synthetic detergents solve the problem of scum formation.

Synthetic detergents are surface active agents and are called “soapless soaps.”

Like soap, detergents contain both hydrophilic (H2O soluble) and hydrophobic
(oil solution) parts.

An example of a detergent is alkyl benzene sulphonates i.e.

CH3 – (CH2)n – CH2 𝑆𝑂3− Na+

However, the major disadvantage of alky benzene sulphonate detergents it that,

they contain so many branches which are non-biodegrable and this can be
dangerous if re-supplied into drinking H2O.

This can be solved by making detergents with no branching (i.e. linear alkyl
group).

TYPES OF DETERGENTS
i) CATIONIC DETERGENTS
These carry positive heads e.g. hexadecyl trimethyl ammonium bromide.
They are made by reacting amines with alkyl halides.

They are used in making air conditioners.

Example:
C15H31CH2NH2 – Br + 3CH3Br C15H31CH2+ N (CH3) 𝐵𝑟 − + 2HBr
In H2O it behaves as;

C15H31CH2+ N (CH3) 𝐵𝑟 − C15H31CH2+ N(CH3)3 + 𝐵𝑟 −

ii) ANIONIC DETERGENTS

219
 These carry negative heads. They are made from benzene by alkylation,
sulphonation and neutralization reaction e.g. sodium-4-dodecyl benzene
sulphonate.

These are used in the manufacture of both pastes and shampoos.

Anionic detergents can also be made from straight chain alcohol (C10 – C14)

iii) NON-IONIC DETERGENTS

These are neutral in H2O i.e. the head carries no charge i.e. they are not
dissociated e.g. CH3(CH2)10CH2 – (OCH2CH2)8 –OH, ethoxylate made from
long chain alcohols with ethoxides.

Example:
CH3(CH2)10CH2-OH + 8CH2CH2 CH3(CH2)10(OCH2CH3)8 –OH

O
They are used as liquid detergents.

The action of detergents can be improved by addition of the following

which constitute the bulk of the detergents.
a) Inorganic phosphates: Are added to soaps to remove any soluble
Ca2+ or Mg2+ in H2O as Ca2+ or Mg2+PO3− 4 .

b) Sodium peroxoborate: This is added to act as a bleaching agent.

They make clothes appear bright. They release H2O2 in H2O which
bleaches.

c) Sodium sulphate: This is added mainly to increase the bulk of the

powder.
Note:
i) The major disadvantage of detergents containing phosphates is that they
cause pollution in rivers, dams, and lakes. (Phosphates are used as food by
algae so their presence promote the growth of algae causing foaming of
H2O thus polluting it.

ii) Detergents are better than soaps because the can be used in any type of
H2O i.e. there is no formation of scum.
END

220